Gas Separation

S. Kasthurirengan
CCT, IISc, Bangalore

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Plan
• Introduction
• Different methods for Gas Separation
-Membrane separation,
-Adsorption,
-Absorption,
-Fractional Distillation
• Rectification Columns Working
• McCabe –Thiele method for Distillation Columns
• Air Separation Systems
• Practical Systems

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 Introduction
In an environment, we normally come across the three states of matter namely,
solid, liquid and gas.

Of these, the gas component arises due to the evolution of gases from various solid
and liquid substances.

Examples:

The liquid is in equilibrium with its vapour and the pressure exerted by the
vapour is known as vapour pressure.

The solid has a coverage of vapour on its surface and also on its internal parts
when it is porous.

Since the environment contains various substances, we always have a gas mixture
only.

For practical
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applications, we need them as pure separate components
TKM_L1_GasSeparationMethods 3
 …Contd.
Major industrial applications of low temperature processing
involves separation and purification of gases.

Distillation of Liquid Air, gives O2, N2, Ar, Kr and Xe.

Helium which is commercially obtained from natural gas is also

separated by a low temperature process.

Hydrogen from Coke oven gas is separated at low temperatures

Important aspects of gas separation and purification are

presented here.
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How do we separate the Gas Mixtures
 Gas Separation is the process of separating a mixture of gas
into its individual components.

 Gas separation deals with not only separating the

components from the mixture but also purifying the
components.

 Several methods can be adopted and they are:

 Membrane Separation
 Adsorption
 Absorption
 Distillation

 We will discuss the different methods given above.

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(Synthetic) Membrane Separation
• Membranes are porous structures.

• Liquids and gases can go through them. However, not all gas
molecules can flow thro the membranes.

• An artificial membrane, or synthetic membrane, is a

synthetically created membrane with porous structure and is
usually used for separation purposes in laboratory or in industry.

• Different polymeric membranes are : Polysulfone (PS),

Polyethylene (PE), Polytetrafluoroethylene (PTFE), Polypropylene
(PP).

• The membranes allow only a certain size of gas molecules to

pass through them.

• In the figure allows only Gas A to pass and hence the separation
occurs.

• For example,
08/26/2023 a thin sheet of palladium allows H2 to pass
TKM_L1_GasSeparationMethods 6
through.
Separation by ADsorption
• ADsorption is the physical or chemical process in which
a certain type of gas molecules are adhered to the
adsorbing surface.

• Since it is a surface phenomenon, it is called as

ADSORPTION.

• If the bulk of the material is involved, it is known as

ABSORPTION.

• Adsorption can be either Physi-sorption or Chemi-

sorption.
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Physisorption  Physical Adsorption
• These are relatively weak forces that attract the neutral molecules to
one another in gases, or liquefied and solidified gases. Ex: H2 bonding
in Water.

• Van der Waal forces are involved in adhering the gas molecules.

• The enthalpy is quite low . The values are ~20 to 40 kJ/mole.

• This effect decreases with increase in temperature.

• Low activation energy needed.

• Multilayer formation on the surface possible.

• The08/26/2023
process is reversible. TKM_L1_GasSeparationMethods 8
Chemisorption  Chemical Adsorption
• In chemisorption, a chemical bonding occurs between the
molecules and the adsorption surface. As an example, we can
see the pumping of H2 gas molecules by Zr-V-Fe getter.

• The enthalpy is quite high . The values are 80 to 240 kJ/mole.

• This effect increases with increase in temperature.

• High activation energy needed.

• Mostly monolayer ins involved.

• The08/26/2023
process is generallyTKM_L1_GasSeparationMethods
irreversible. 9
Separation by Adsorption
• In the case of gas separation, mostly
one considers physi-sorption methods

• The adsorbate in the figure adheres

only Gas A to its surface and the
vapour phase is enriched in Gas B.

• Hence, the gas separation occurs

• The effect is also enhanced at lower

temperatures.

• For example, finely divided nickel can

adsorb hydrogen on to its
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TKM_L1_GasSeparationMethods 10
ABsorption
• Absorption is a 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.

• Removal of a liquid by using Tissue paper is an adsorption

process.

• 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 process helps

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TKM_L1_GasSeparationMethods
Cryogenic Distillation
• The separation of a mixture can be done both at RT and at cryogenic temperatures.

• In the conventional distillation of two RT liquids, the low Boiling Point (BPt) component
is completely boiled off, before the high BPt component is evaporated. Exaample:
Distillation of C2H5OH (Ethanol) and water.

• In the case of cryogenic fluids their BPts are low. When they are well separated, it is
much easier to separate them. When cooled by the cryogenic fluid, one of them will be
a liquid, while the other will remain as a gas. Ex: Helium /N2 mixtures

• If the boiling points are close to each other, then it is not easy to separate them as
before. But they can be separated by the method of distillation.

• If the distillation process occurs at cryogenic temperatures, it is known as Cryogenic

Distillation, otherwise, it is normal distillation.

• The commercial production of gases like O2, N2, Argon, Neon, Krypton & Xenon is
obtained by cryogenic distillation of Liquid Air.
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Is Mixing of Gases Reversible?
• 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.
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Ideal Gas Separation System
• It is clear that the mixing of two
gases is an irreversible process
because 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.
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• The left piston (red)allows only ….Contd.
the Gas A to pass through, but
not the Gas B

• 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.

• The work of separation is the

work required to compress each
gas from p1a or p1b to pm at a
constant temperature Tm
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• The entire process is reversible. ….Contd.
• 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.

• Thermodynamically each gas is

compressed reversibly and
isothermally from its partial
pressure to the mixture pressure.

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Work Required for Ideal Gas Compression

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Work Requirement for Ideal Gas Separation System

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 …Contd.

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 …Contd.

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Work needed for separating the gases from Air at 300K

• We observe that as the component becomes smaller more work

is needed to separate that component to pure state.
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GIBBs Phase Rule
• Gibbs Phase Rule was formulated by Josiah
Willard Gibbs, an American physicist, in
1878.

• If 𝐹 is the degrees of freedom or the

minimum number of Intensive properties
required to define the thermodynamic state
of a system, then by Gibbs Phase Rule

𝐹=𝐶−𝑃+2

• For example, for gaseous N2, we have

𝐶=1 and 𝑃=1 Therefore, 𝐹=2 .

• These can be pressure and temperature or

pressure and specific volume.
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GIBBs Phase Rule for 2 component system
• For a mixture of Gas A and Gas B in single
phase, we have 𝑃=1 and 𝐶=2.

• Using the Gibbs Phase Rule,

𝐹=2−1+2=3

• These properties can be pressure,

temperature and mole fraction of one of the
components.
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Phase Equilibrium Curve
• In general, single phase single component system is
governed by 2 variables namely pressure and
temperature.

• But for a 2 component mixture at a given pressure,

the mole fractions of components in vapor and
liquid phases change with the temperature.

• Variation of mole fraction (y) with temperature (T)

at a constant pressure (p) is given by Temperature
composition diagram or Phase – equilibrium curve.
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Temperature Composition Diagram

Case 1. Critical Case 2. One of the

Case 3. Azeotropic
Pressures (pc) of both components has pc less
mixture
components are more than the pressure p.
than pressure p

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Temp – Composition Diagram of N2–O2 mixture

• Temperature – Composition diagram for mixture of

O2 and N2 at a given constant pressure.
(components on the x –axis are interchanged )

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Temp – Composition (expt) Curves of N2-O2 Mixture at different Pressures

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 Details of Temp-Composition curves

• Upper curve (Red):

Dew line.

• Lower curve (violet):

Bubble line.

• The area formed by these

curve lines:
two phase region

08/26/2023 TKM_L1_GasSeparationMethods 28
 …contd.
• Consider a Temperature
composition diagram for a mixture
of O2 and N2 at a pressure of 1
atm.

• Let the initial state of the mixture

be at point 1 as shown in the
figure.

• Since T > 90 K for point 1 , the

mixture exists as gaseous phase.

• Let the mixture be cooled at

constant pressure.
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 …contd.
• When the temperature of the mixture
reaches point 2g, the mixture starts
condensing.

• The point 2g lies on the dew line and

the first drop or the dew appears in
the mixture.

• Therefore, the mixture at point 2g is a

two –phase mixture with liquid –
vapor phases in equilibrium.

• Condensate liquid has mole fractions

of both high boiling and low boiling
liquids
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 …contd.
• Liquid content is obtained by a
constant temperature line
about the point 2g.

• Extending a constant
temperature line about 2g, it
intersects the bubble line at
point 2f.

• 2g and 2f denote the mole

fractions of higher BP liquid
(O2) in gaseous and liquid
phases respectively.
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 …contd.
• The mixture is now cooled to
a point 3.

• The line extended to the left

side intersects the Dew line at
the point 3g.

• And, the line extended to the

right side intersects the
bubble line at the point 3f.

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• On further cooling of the mixture, the …contd.
temperature reaches a point 4f .

• At this point, most of the high boiling

component of the vapor is condensed.

• Extending a constant temperature line about

the point 4f to left, we have 4g.

By cooling of the mixture

• The % of low BP component in liquid has

increased

• The %of high BP component has decreased in

vapor and liquid phases.

• The mole fraction of mixture is unchanged,

but the mole fractions in vapor and liquid
phases have changed
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Importance of difference in Boiling Points
• Consider two gas mixtures AB and
CD

• The boiling point difference of the

mixture AB is less than that of the
mixture CD.

• The separation is more effective

when the difference in the boiling
points is more.

• For such mixtures, almost pure

product is obtained in one or two
condensations
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 Enthalpy – Composition Diagram
• The enthalpies of the vapor and the
liquid fractions are dependent on the
- Temp of the mixture.
- Relative mole fractions of the
components.

• In a mixture, the enthalpy calculations

for liquid and vapor mole fractions are
done using the Enthalpy composition
diagrams.

• These isotherms have finite slope

indicating that condensation or boiling
is a NON- ISOTHERMAL process.
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Rectification Process
• Consider a mixture of N2
and O2 at 1 atm.

• Let the initial condition of

the mixture be at point 3
as shown in the figure.

• The compositions of the

higher boiling liquid at
point 3 are given by

08/26/2023 TKM_L1_GasSeparationMethods 36
 …Contd.
• Now, consider the
rectification of mixture with
composition at point 3f.

• Again, extending the

constant temperature lines
about point 3f, we have 3ff
and 3fg respectively.

• The liquid composition of

higher boiling liquid at
point 3ff is given by
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 …Contd.
• Consider the rectification of
mixture with composition
at point 3g.

• Again, extending the

constant temperature lines
about point 3g, we have 3gf
and 3gg respectively.

• The vapor composition of

lower boiling component at
point 3gg is given by
08/26/2023 TKM_L1_GasSeparationMethods 38
 …Contd.
• Thus, the rectification of
mixture at point 3, the vapor
is enriched in the lower
boiling component (here, N2).

• Similarly, the liquid is

enriched in high boiling
component (here, O2).

• This process forms the

fundamental step for the
rectification column.

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 Next Topic

Rectification Column Working

08/26/2023 TKM_L1_GasSeparationMethods 40
 Thank You

08/26/2023 TKM_L1_GasSeparationMethods 41