(18!5!1) NPTEL - Gas Separation

18
Earlier Topics
Introduction to Cryogenic Engineering
Properties of Cryogenic Fluids
Properties of Materials at Cryogenic Temperature
Gas Liquefaction and Refrigeration Systems
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
Current Topic
Topic : Gas Separation

Basics of Gas Separation
Ideal Gas Separation System
Properties of Mixtures and the Governing Laws
Principles of Gas Separation
Rectification and Plate Calculations
The current topic will be covered in 7 to 10
lectures.
Tutorials and assignments are included at the end
of each lecture.
Outline of the Lecture
Topic : Gas Separation
Basics of Gas Separation

Gas Separation methods
Ideal Gas Separation System
Work requirement
Introduction
As mentioned earlier, cryogenic industry is huge

owing to the various applications of the
cryogens, both in liquid and gaseous states.
For example, the use of inert gases like argon in

chemical and welding industries has increased in
the recent past.
Liquid Nitrogen is used as precoolant in most of

the cryogenic systems. Also, cryogens like LOX,
LH2 are used in rocket propulsion.
Introduction
In the recent past, LH2 is being considered as a

fuel for an automobile.
Production of Ammonia in RCF industry, requires

separation of purge gases like Nitrogen, Argon
and other inert gases at cryogenic temperatures.
For most practical purposes, Air is considered as

a mixture of 78% N2 + 21% O2 + 1% Ar.
The other ingredients are Helium, Neon, Krypton

etc. which occur in negligible quantities.
Introduction
Air is the raw material for the production of most

of the gases and the process of separation of
any gas mixture into its individual components is
called as Gas Separation.
In other words, this topic Gas Separation

deals with separation of various gas mixtures
and their purification.
Gas Separation
Different techniques of gas separation commonly

used are
Synthetic membranes
Adsorption
Absorption
Cryogenic distillation
Gas Separation
Membrane
B B A BA
A A B B
B B BA
A
A B
Piston
A BA
ABB
BA
B B
A
A
A
A
A
A
A
Gas Separation
Synthetic membranes
are the porous media
which allow only a
certain gas molecules to
pass through.
The membrane in the

figure allows only Gas A
to pass and hence the
separation occurs.
For example, a thin

sheet of palladium allows
H2 to pass through.
Gas Separation
B B A B B B B
A A B AA A B
B
A B B B B
A
A B
B A A
A B B A B A
Adsorption is the physical

processes in which only a
certain kind of gas molecules
are adhered to the adsorbing
surface.
The adsorbate in the figure

adheres only Gas A to the
surface and hence the
separation occurs.
For example, finely divided

Nickel adsorbs hydrogen on to
its surface.
Adsorbate
B B A B B A B
A B B AA A B
B
A B A B B
B
B A A B
A A A
A
A
A A AA A
A
Adsorbate
10
Gas Separation
Absorption is a chemical process in which a

substance in one physical state is taken into
other substance at a different physical state.
For example, liquids being absorbed by a solid or

gases being absorbed by a liquid.
When an incoming stream containing CO2 is

passed through a solution of Sodium hydroxide,
the later absorbs the gas and hence decreases
the CO2 content in the outgoing stream.
Hence, this chemical process helps in the

separation of the mixture.
11
Gas Separation
Qout,
Distillation is a process of separation

based on the differences in the
volatilities (boiling points).
If the process of distillation occurs

at cryogenic temperatures, it is
called as Cryogenic Distillation.
The commercial production of gases

like O2, N2, Argon, Neon, Krypton &
Xenon is obtained by cryogenic
distillation of Liquid Air.
77 K
B
A+B
A
Qin,
90 K
12
Gas Separation
The separation of a mixture can be done at both

room temperature and cryogenic temperature.
For example in the case of Air, the following

processes are possible.
Air(300K)
Separation
Liquefaction
LOX(90K)
LN2(77K)
Cryogenic Separation
O2(300K)
N2(300K)
LOX(90K) LN2(77K)
Room Temp. Separation
13
Gas Separation
Some of the advantages of Cryogenic separation

over Room Temperature separation are
The separation at lower temperatures is most

economical (explained in further slides).
There is an increased difference in the boiling

points of the ingredients (explained in further
slides).
A large quantities of the gas can be separated.
A high purity of the gas can be obtained.

14
Is Gas Mixing Reversible?

A A AA BB B
B
A AA A
BBBB
A AA A
BBB
A AA
B B BB
B B B A B BB
A A A B A A
B B B
B B B B B
A
A
A
A
A A AA BB B
B
A AA A
BBBB
A AA A
BBB
A AA
B B BB
Consider a closed chamber

filled with Gas A and Gas B as
shown in the figure.
Initially, the gases are

separated by an impervious
wall.
If the wall is removed, the

gases would mix.
However, the replacement of

wall would not result in the
separation of gases.
15
Gas Separation
It is clear that the mixing of two different gases

is an irreversible process because unmixing or
separation of the mixture requires work input.
The system in which all the processes are

reversible is called as an Ideal System.
Although in reality such a system does not exist,

a system can be conceived to serve the required
purpose as explained in the next slide.
16
Ideal Separation System

Tm, pm
B B A B B B
A
A A B A A
A B
B B B B
B A
A A A A
Consider a closed
chamber filled with a
mixture of Gas A and
Gas B as shown.
The temperature and

mixture pressure are
Tm and pm
respectively.
The partial pressures

of Gas A and Gas B
are given by p1a and
p1b respectively.
p1a, p1b
17

Tm, pm
B B A B B B
A
A A B A A
A B
B B B B
B A
A A A A
The chamber has two

frictionless opposing
pistons made of semi
permeable membranes
as shown in the figure.
As seen earlier, a semi

permeable
membrane is a film
which allows only one
kind of gas to pass
through but not the
other.
p1a, p1b
18

Tm, pm
B B A B B B
A
A A B A A
A B
B B B B
B A
A A A A
The left piston (red)

allows only the Gas A
to pass through, but
not the Gas B.
B AB
A B A
B
A B
B
A
A B A
Similarly, the right

piston (green) allows
only the Gas B to pass
through, but not the
Gas A.
When both pistons are

moved inward, the
mixture is separated.
p1a, p1b
A
A
A
A
A A A A
A A A
A A AAA
A A A A
B
B
B
BB
B B
B B
BBB
B
19

Tm, pm
B B A B B B
A
A A B A A
A B
B B B B
B A
A A A A
p1a, p1b
QR
WA
A
A
A
A
B AB
A B A
B
A B
AB
A B A
B
B
B
BB
WB
Since the processes are

reversible, the system
interacts with the
surroundings to
maintain a constant
temperature.
The work of separation
is the work required to
compress each gas
from p1a or p1b pm
at a constant
temperature Tm.
20

Tm, pm
B B A B B B
A
A A B A A
A B
B B B B
B A
A A A A
Since the left piston is

permeable to Gas A,
the Gas A exerts no
pressure on the left
piston.
WB
Similarly, the gas B

exerts no pressure on
the right piston.
p1a, p1b
QR
WA
A
A
A
A
B AB
A B A
B
A B
AB
A B A
A A A A
A A A
A A AAA
A A A A
B
B
B
BB
B B
B B
BBB
B
When both the pistons

are moved inward, the
mixture is separated
at constant Tm.
21

Tm, pm
A A A A
A A A
A A AAA
A A A A
A
A
A
A
B AB
A B A
B
A B
B
A
A B A
B B
B B
BBB
B
The entire processes

are assumed to be
reversible.
The process is
reversed due to the
difference in the
concentrations of Gas
A and Gas B.
Hence, the mixing of

the gases would move
the pistons away and
produce work.
B
B
B
BB
22

Tm, pm
A A A A
A A A
A A AAA
A A A A
B
B
B
BB
WB
The final condition is a

system with a mixture
of Gas A and B at pm
and Tm.
Also, the partial

pressures of Gas A
and B are p1a and p1b.
QR
WA
A
A
Tm, pm
A
A
B AB
A B A
B
A B
AB
A B A
B B A B B B
A
A A B A A
A B
B B B B
B A
A A A A
p1a, p1b
The Work produced in

this mixing process is
same as the Work
done to separate at
constant Tm.
B B
B B
BBB
B
23

Initial
Tm, pm
B B A B B B
A
A A B A A
A B
B B B B
B A
A A A A
p1a, p1b
Final
A A A A
A A A
A A AAA
A A A A
Tm, pm
B B
B B
BBB
B
Gas Const T
p1a pm
A
p1b pm
B
In other words, thermodynamically each gas is
compressed reversibly and isothermally from
its partial pressure to the mixture pressure.
24

Initial
Tm, pm
B B A B B B
A
A A B A A
A B
B B B B
B A
A A A A
p1a, p1b
Final
A A A A
A A A
A A AAA
A A A A
Tm, pm
B B
B B
BBB
B
Gas Const T
p1a pm
A
p1b pm
B
In order to understand the process of
compression, say for a Gas A, from p1a to pm,
the following analysis is done.
25
Let the mol. wt. of Gas A and Gas B be molwa

and molwb respectively.
Number of moles of Gas A is given by na = ma / molwa
Similarly, number of moles of Gas B is nb = mb / molwb
Then total number of moles in the mixture nm is

nm= na + nb
ya = na / nm
yb = nb / nm
Then the ratios

and
are the
mole fractions of Gas A and Gas B respectively.
26

Initial
Tm, pm
B B A B B B
A
A A B A A
A B
B B B B
B A
A A A A
p1a, p1b
Vtot
p1aVtot= na Tm
p1bVtot= nbTm
( p1a + p1b )Vtot = ( na + nb ) Tm

p1a + p1b =
pm
Final
A A A A
A A A
A A AAA
A A A A
Tm, pm
Va
pmVa= na Tm
B B
B B
BBB
B
Vb
pmVb= nbTm
Va na
=
Vb nb
The volume occupied by the each of the gas is

directly proportional to its number of moles.
27
From the earlier lectures, the work requirement

for a unit mass of gas compressed isothermally is
given by
Wi
= Tm ( s1 s2 ) ( h1 h2 )
m
The net ideal work requirement of the separation

process is the sum of the ideal work requirement
by Gas A and Gas B.
Mathematically,
Dividing the above equation W W

Wi ,b
i ,a
i
+
by the mass of the mixture =
mm
mm
mm
mm, we get
Wi = ( Wi ,a ) + ( Wi ,b )
28

Wi Wi ,a Wi ,b
=
+
mm
mm
mm
The total mass of mixture mm is the sum of mass

of Gas A and Gas B.
ma + mb
Mathematically, we have m=
m
Rearranging the terms, we can write the above

equation as
Wi Wi ,a ma Wi ,b mb
=
mm ma mm mb mm
Here, ma and mb are the mass of the Gas A and
Gas B respectively.
29
Wi Wi ,a ma Wi ,b mb
=
mm ma mm mb mm
The work requirement for each of the individual
gas is given by the following equations.
Wi ,a
Wi ,b
= Tm ( s1b s2b ) ( h1b h2b )
= Tm ( s1a s2 a ) ( h1a h2 a )
ma
mb
Substituting and rearranging, we get
ma
( ( s1a s2 a ) ( h1a h2 a ) )
Wi
mm
= Tm
mm
+ mb ( ( s1b s2b ) ( h1b h2b ) )

m
30
ma
( ( s1a s2 a ) ( h1a h2 a ) )
Wi
mm
= Tm
mm
m
+ b ( ( s1b s2b ) ( h1b h2b ) )
m
It is clear that the work requirement decreases

with the decrease in the temperature.
Hence, the separation of mixtures at the

cryogenic temperatures is most economical.
The subscripts 1 and 2 denote the initial and the

final conditions respectively.
31
ma
( ( s1a s2 a ) ( h1a h2 a ) )
Wi
mm
= Tm
mm
m
+ b ( ( s1b s2b ) ( h1b h2b ) )
m
It means that for each gas, s1 and h1 are at the

partial pressure before the separation. And s2
and h2 are at mixture pressure after the
separation of the mixture.
For the sake of understanding, let us first

evaluate only entropy and enthalpy terms for
each of the gases.
32
For an ideal gas, the specific entropy s and

specific enthalpy h can be expressed as
s = c p ln T R ln p + sr
=
h c pT + hr
where, sr and hr are some reference values.
Hence, s and h for Gas A are given by

s1a = c pa ln Tm Ra ln p1a + sra
=
h1a c paTm + hra
s2 a = c pa ln Tm Ra ln p1a + sra
=
h2 a c paTm + hra
33
The entropy and enthalpy term for Gas A is as

given below.
( ( s1a s2a ) ( h1a h2a ) )
Substituting, we get
(c
pa
ln Tm Ra ln p1a + sra c pa ln Tm + Ra ln pm sra )

( c paTm + hra c paTm hra )
pm
Ra ln
( ( s1a s2a ) ( h1a h2a ) ) =
p1a
Also, for Gas B
pm
Rb ln
( ( s1b s2b ) ( h1b h2b ) ) =
p
1b
34

pm
Ra ln
( ( s1a s2a ) ( h1a h2a ) ) =
p1a
pm
Rb ln
( ( s1b s2b ) ( h1b h2b ) ) =
p
1b
Substituting, we
get the ideal
work
requirement as
ma
( ( s1a s2 a ) ( h1a h2 a ) )
Wi
mm
= Tm
mm
+ mb ( ( s1b s2b ) ( h1b h2b ) )

m
Wi
mm
ma
pm mb
pm
Tm
Ra ln
+
Rb ln

p1a mm
p1b
mm
35
Since the process occurs at constant volume Vm,

using an ideal gas equation we can write
pmVm= nmTm
p1aVm= na Tm
p1bVm= nbTm
Dividing one over the other, we have

pmVm nmTm
=
p1aVm na Tm
pmVm nmTm
=
p1bVm nbTm
pm nm
1
= =
p1a na ya
pm nm 1
= =
p1b nb yb
Where ya and yb are the mole fractions of Gas A

and Gas B respectively.
36
The ideal gas equation can also be expressed in

terms of the mass of the gas as shown below.
pmVm= nmTm
pmVm
=
p1aVm= na Tm
p1bVm= nbTm
mm
ma
mb
p1aVm
Tm =
Tm =
Tm
p1bVm
molwa
molwm
molwb
pmVm = mm RmTm
p1aVm = ma RaTm
p1bVm = mb RbTm
In general, Ra =
and 8.314 J / mol K
=
molwa
Here and R are the Universal Gas Constant

and Specific Gas Constant respectively.
37
From the earlier slide, using the ideal gas

equation in terms of the gas mass, we have
pmVm = mm RmTm
p1aVm = ma RaTm
p1bVm = mb RbTm
Dividing one over the other, we have

pmVm mm RmTm
=
p1aVm ma RaTm
pmVm mm RmTm
=
p1bVm mb RbTm
pm mm Rm 1
pm mm Rm
1
=
=
=
=
yb
p1a ma Ra
ya p1b mb Rb
ma Ra
= Rm ya
mm
mb Rb
= Rm yb
mm
38

pm
1
=
p1a ya
Wi
mm
pm
1
=
p1b yb
ma Ra
= Rm ya
mm
mb Rb
= Rm yb
mm
ma
pm mb
pm
Tm
Ra ln
+
Rb ln

p1a mm
p1b
mm
Substituting, we have
Wi
mm
1
1
RmTm ya ln + yb ln pmVm= mm RmTm= nmTm
ya
yb
1
1
Wi
=
Tm ya ln + yb ln
nm
ya
yb
39
The ideal work of separation per mole of mixture

(Gas A and Gas B) is given by
1
1
Wi
=
Tm ya ln + yb ln
nm
ya
yb
On the similar lines, if the mixture is composed

of three different gases, say Gas A, Gas B and
Gas C, the ideal work of separation per mole of
mixture is given by
1
1
1
Wi
=
Tm ya ln + yb ln + yc ln
nm
ya
yb
yc
40
Generalizing the above equation for a mixture of

N constituents, we have
N
1
Wi
= Tm y j ln
y
nm
j =1
j
where yj is the mole fraction of jth component.
Similar to the Liquefaction systems, the Figure

of Merit (FOM) is defined as given below.
Wi
nm
=
FOM =
W
nm
Wi
mm
W
mm
41
Summary
Different techniques employed are Synthetic

membranes, Adsorption, Absorption and
distillation.
The separation can be done at both room

temperature and cryogenic temperature.
In an Ideal system all the processes are

reversible and the work requirement in an ideal
gas separation is called as an Ideal Work.
42
Summary
Ideal work requirement per mole of mixture to

separate a mixture with N constituents is given
by
N
1
Wi
= Tm y j ln
y
nm
j =1
j
where yj is the mole fraction of jth component.
43
A self assessment exercise is given after

this slide.
Kindly asses yourself for this lecture.
44
Self Assessment
1. Air is considered as a mixture of ________.
2. Thin sheet of palladium allows only __ to pass
through.
3. ________ is the processes in which only a
certain kind of gas molecules are adhered.
4. ___ is a chemical process for gas separation.
5. ______ separation is most economical.
45
Self Assessment
6. In an ideal system, each gas is compressed from
its ____ to the ______.
7. In an ideal system
(( s
1a
s2 a ) ( h1a h2 a ) ) is ______.
8. The Specific Gas constant for a Gas A (Ra) is

______.
46
Answers
1. 78% N2 + 21% O2 + 1% Ar
2. Hydrogen
3. Adsorption
4. Absorption
5. Cryogenic
6. partial pressure, mixture pressure

7. G( ( s1a s2 a ) ( h1a h2 a ) ) =
Ra ln ( pm / p1a )
8. FRa = / mola
47
Thank You!
48

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18

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

Topic : Gas Separation

Outline of the Lecture

Topic : Gas Separation

Basics of Gas Separation

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

As mentioned earlier, cryogenic industry is huge

For example, the use of inert gases like argon in

Liquid Nitrogen is used as precoolant in most of

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

In the recent past, LH2 is being considered as a

Production of Ammonia in RCF industry, requires

For most practical purposes, Air is considered as

The other ingredients are Helium, Neon, Krypton

Air is the raw material for the production of most

In other words, this topic Gas Separation

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

Different techniques of gas separation commonly

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

The membrane in the

For example, a thin

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

Adsorption is the physical

The adsorbate in the figure

For example, finely divided

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

Absorption is a chemical process in which a

For example, liquids being absorbed by a solid or

When an incoming stream containing CO2 is

Hence, this chemical process helps in the

Distillation is a process of separation

If the process of distillation occurs

The commercial production of gases

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

The separation of a mixture can be done at both

For example in the case of Air, the following

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

Some of the advantages of Cryogenic separation

The separation at lower temperatures is most

There is an increased difference in the boiling

A large quantities of the gas can be separated.

A high purity of the gas can be obtained.

Is Gas Mixing Reversible?

Consider a closed chamber

Initially, the gases are

If the wall is removed, the

However, the replacement of

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

It is clear that the mixing of two different gases

The system in which all the processes are

Although in reality such a system does not exist,

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

Ideal Separation System

The temperature and

The partial pressures

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

Ideal Separation System

The chamber has two

As seen earlier, a semi

Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay

Ideal Separation System

The left piston (red)

Similarly, the right