11-Oct-14

Liquefied Gases
Gas Normal boiling point, K (oC)
Helium-4 4.2 (-268.9)
Hydrogen 20.3 (-252.9)
Neon 27.1 (-246.1)
Nitrogen 77.3 (-195.8)
Air 78.9 (-194.3)
Fluorine 85.0 (-188.1)
Argon 87.3 (-185.9)
Oxygen 90.2 (-183)
Methane 111.7 (-161.5)
Ethane 184.5 (-88.6)
Propane 231.1 (-42.1)
Dr. Tamer Samir © 10

Liquefaction of Gases
Critical Temperature
Critical Temperature: The
highest temperature at which Fluid Region
(Supercritical Fluid)
it is possible to liquefy a gas by Liquid Region
pressure alone. For a gas, no Critical
Fusion Curve

Pc Point
liquefaction occurs above its
critical temperature whatever rve
Cu
its pressure
Pressure

on
Solid Region ati
o ri z
p
Va
Gas Region

Triple
rve Point (Vapor)
Cu
ti on
ma
bli
Su

Temperature Tc

P–T plot for a pure substance

Dr. Tamer Samir © 11

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 11-Oct-14

Liquefaction of Gases
Critical Points of Different Substances (1)
Substance TC, C PC, atm
Helium -267.96 2.24
Hydrogen -239.95 12.8
Oxygen -118.15 49.8
Nitrogen -147.15 33.5
Fluorine -129.15 51.5
Argon -122.15 48.1
Carbon dioxide 31.05 72.8
Ammonia 132.35 111.3
Chlorine 143.85 76
Water 373.95 217.7
Methane -82.65 45.4
Ethane 32.25 48.2
Propane 96.65 42
Dr. Tamer Samir © 12

Liquefaction of Gases
Critical Points of Different Substances (2)

In the absence of data, a

rule of thumb is that
TC 1.6 TNBP (All gases except
helium)
TC 1.2 TNBP (helium)

TNBP:Normal boiling point

(boiling point at 1 atm)

TC : Critical temperature

Dr. Tamer Samir © 13

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Liquefaction of Gases
Liquefaction Versus Refrigeration (1)

Expansion Expansion

Make-up
Liquid

A Refrigerator A Liquefier

Dr. Tamer Samir © 14

Liquefaction of Gases
Liquefaction Versus Refrigeration (2)
A refrigerator is a machine for making cold. A liquefier is a
refrigerator that produces a cold liquid that is then drawn off. The
thermodynamics is the same for both a refrigerator and a
liquefier. The engineering is quite a bit different:
1. A refrigerator operates as a closed loop. There is no
accumulation or withdrawal of product in a refrigerator. The
mass flow rate of the refrigerant is the same at all points of
the cycle. A refrigerator can certainly make a liquid coolant.
This liquid refrigerant will be evaporated continuously by the
heat added at the low temperature sink and the vapor will be
returned to complete the cycle.
2. A liquefier is an open system. A liquid product is removed, and
an equivalent make-up stream must be added.
Dr. Tamer Samir © 15

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Liquefaction of Gases
Ways of Cooling

Cooling in general can be achieved by:

1. Expansion (sudden pressure reduction)
a) Throttling using Joule-Thompson effect (Isenthalpic expansion)
b) Turbine expanders (Isentropic expansion)

2. Heat exchange with a cooler stream (Refrigeration)

The second method usually involves having a cooler stream which

usually achieves its low temperature by the first method (expansion)

Dr. Tamer Samir © 16

Liquefaction of Gases
Joule-Thompson Effect

The Joule–Thomson effect describes the temperature change of a

gas or liquid when it is forced through a valve or porous plug while
kept insulated so that no heat is exchanged with the environment.
1 2

H  0 (Isenthalpic process)
P1 > P 2
The J–T coefficient is usually denoted by μJ-T and
is given by
 T 
 J T   
 P  H
 0 (cooling happens when pressure decreases)
 0 (heating happens when pressure decreases)
 0 (No change in temperature happens when pressure decreases)
Dr. Tamer Samir © 17

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 11-Oct-14

Liquefaction of Gases
Joule-Thompson Effect (2)

Dr. Tamer Samir © 18

Liquefaction of Gases
Joule-Thompson Effect (3)
Comments (1)
• All gases has a +ve Joule-Thompson
coefficients at ambient temperature
(they will cool if throttled) except He,
H2 & Ne, which have -ve J–T
coefficients at ambient temperature
(they will warm when throttled).
• For a given pressure drop during
throttling, the drop in temperature
is higher at lower temperatures
compared to higher temperatures.
• Gases cannot be liquefied by
throttling (i.e., exit condition will
not be in two phase region), unless
the temperature of the gas is first lowered sufficiently. This fact is very important in
the liquefaction of gases. In order to liquefy these gases, they have to be first
compressed to high pressures, cooled isobarically to low temperatures and then
throttled, so that at the exit a mixture of liquid and vapor can be produced.
Dr. Tamer Samir © 19

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Liquefaction of Gases
Joule-Thompson Effect (3)
Comments (2)
• Joule-Thompson coefficient of ideal gas is zero (no heating or cooling happens
when the gas undergoes expansion (throttling))

• The more non-ideal the gas is, the better for J-T expansion (more
cooling/liquefaction).
• Since a liquid is considered the most non-ideal gas, liquid state is preferred before
introducing to J-T expansion. This is the reason we try to achieve the liquid state
(by precooling) before the J–T expansion.

•Among liquids, the highly polar fluids are the most non-ideal. This explains why
ammonia and the fluorocarbons (the R-series refrigerants) are usually chosen as
refrigerants (highly polar)

Dr. Tamer Samir © 20

Liquefaction of Gases
Turbine Expanders (1)
Steady flow expansion of a high pressure gas through a turbine 1
or an expansion engine results in a net work output with a
resulting decrease in enthalpy. This decrease in enthalpy leads to
a decrease in temperature. In an ideal case, the expansion will be
reversible adiabatic (isentropic), however, in an actual case, the
expansion can be adiabatic but irreversibility exists due to fluid
friction. 2

Ws  H

S   T 
 


P S

Dr. Tamer Samir © 21

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 11-Oct-14

Liquefaction of Gases
Turbine Expanders (2)
Comments (1)
• μS is always +ve (i.e. isentropic expansion will result always in cooling)
• μS – μJ-T =+ve =v/CP (more cooling with upon expansion using expanders compared to
joule-Thompson valves)
• However, the difference becomes very small in the following cases:
- For liquids where v ↓ and at lower temperatures and at high pressures.
- Cp → ∞ near the critical points for all fluids.

Therefore, J–T expansion may be indistinguishable thermodynamically from isentropic

expansion (μJT → μS) when:
 The expansion is meant to produce liquid or,
 The expansions occurs near or below the critical point.

Dr. Tamer Samir © 22

Liquefaction of Gases
Turbine Expanders (2)
Comments (2)
• In addition:
Real expansion turbines have difficulty operating in the two-phase region
Real expansion turbines may be only approximately 85% or so of isentropic
Real expansion turbines suffers from that the produced temperature drop decreases as the
initial temperature decreases
 Real expansion turbines with small scale expansion engines have not been developed yet
 Real expansion turbines have some mechanical challenges such as lubrication, seals, …, etc
 Real expansion turbines is much more expensive than J-T devices
In general
 There is no thermodynamic reasons to prefer “real” isentropic expansion turbines over J-T
valves
There are numerous hardware reasons to prefer J-T valves over isentropic expansion
engines
Isentropic expansion engines are preferred only
 at higher temperatures to pre-cool the gas (especially when the temperature is higher
than the inversion temperature)
 for one phase only (No liquids)
At very high flow rate to extract work
Dr. Tamer Samir © 23