Unit – 1

Liquefaction Processes

Air Fractionation & Purification of Gases

 Energy Balance for Open Systems
When the control volume has one entrance and one exit, the same mass flow
rate, 𝑚,ሶ applies to both streams

1 2
∆ 𝐻+ 𝑢 + 𝑔𝑧 𝑚ሶ = 𝑄ሶ + 𝑊ሶ 𝑠
2

Division by 𝑚ሶ gives:
1 2 𝑄ሶ 𝑊ሶ 𝑠
∆ 𝐻+ 𝑢 + 𝑔𝑧 = + = 𝑄 + 𝑊𝑠
2 𝑚ሶ 𝑚ሶ

∆𝑢2
∆𝐻 + + 𝑔∆𝑧 = 𝑄 + 𝑊𝑠
2
𝑢22 − 𝑢12
𝐶𝑝 𝑇2 − 𝑇1 + + 𝑔(𝑧2 − 𝑧1 ) = 𝑄 + 𝑊𝑠
2

Unit 1: Cryogenic Properties of Air

 Entropy
The entropy change of a heat reservoir is given by Q/T, where Q is the
quantity of heat transferred to or from the reservoir at temperature T,
whether the process is reversible or irreversible.

Entropy Changes of an Ideal Gas

𝑇 𝑖𝑔
∆𝑆 𝐶𝑝 𝑑𝑇 𝑃
= න − ln
𝑅 𝑅 𝑇 𝑃0
𝑇0

Unit 1: Cryogenic Properties of Air

 Reversible Cold-Gas Refrigeration Cyc1e
In this cycle, refrigeration temperature follows a
constant pressure process from state 1 to 2.
Coefficient of performance for this cycle results
in
𝑄ሶ 𝑐 /𝑚ሶ
𝐶𝑂𝑃 =
𝑄ሶ ℎ /𝑚ሶ − 𝑄ሶ 𝑐 /𝑚ሶ
ℎ2 − ℎ1
=
𝑇ℎ 𝑠3 − 𝑠4 − ℎ2 − ℎ1
For an ideal gas
h2 – h1 = Cp (T2 - T1)
and at constant pressure, entropy change is
𝑇2
𝑠3 − 𝑠4 = 𝑠2 − 𝑠1 = 𝐶𝑝 𝑙𝑛 ൗ𝑇1
𝑇2
𝑇2 − 𝑇1 ൗ𝑇 − 1
1
𝐶𝑂𝑃 = =
𝑇2 𝑇ℎ 𝑇 𝑇
𝑇ℎ 𝑙𝑛 ൗ𝑇 − 𝑇2 − 𝑇1 ൗ𝑇 𝑙𝑛 2ൗ𝑇 − 2ൗ𝑇 + 1
1 1 1 1

Unit 1: Cryogenic Properties of Air

 Figure of Merit (FOM)
The performance of real refrigerators is compared with the ideal refrigerator is
compared by applying a performance criterion known as the figure of merit,
FOM, defined as
FOM = COP/COPi
where COP is the coefficient of performance of the actual refrigeration system
and COPi is the coefficient of performance of a thermodynamically ideal
system.

Unit 1: Cryogenic Properties of Air

 Liquefaction
Liquefaction is essentially an open-
system process; therefore, for the ideal
liquefaction system, two processes from
the Carnot cycle are utilized, namely, a
reversible isothermal compression
followed by a reversible isentropic
expansion.
The pressure that must be attained at the
end of the isothermal compression for
even an ideal nitrogen liquefaction
system is extremely high-on the order of
70,000 MPa.
It is impossible to attain such pressures
with existing compression equipment.
Applying an energy balance to this ideal cycle shows that the work per unit mass liquefied
is given by
−𝑊ሶ 𝑖 /𝑚ሶ 𝑓 = 𝑇 𝑠1 − 𝑠𝑓 − ℎ1 − ℎ𝑓
Since all of the gas compressed is liquefied in this ideal liquefaction cycle, 𝑚ሶ equals 𝑚ሶ 𝑓 .
Unit 1: Cryogenic Properties of Air
 Ideal Work Requirement
Ideal work requirements for the liquefaction of gases initially at 294 K
and 0.101 MPa

Unit 1: Cryogenic Properties of Air

 Figure of Merit (FOM)
The performance comparison for liquefiers is also the figure of merit.
FOM for a liquefier is normally defined as

−𝑊ሶ 𝑖 /𝑚ሶ 𝑓
𝐹𝑂𝑀 =
−𝑊/ሶ 𝑚ሶ 𝑓

where 𝑊ሶ 𝑖 /𝑚ሶ 𝑓 is the work of compression per unit mass liquefied for the ideal
ሶ 𝑚ሶ 𝑓 is the work of compression per unit mass
liquefaction cycle and 𝑊/
liquefied for the actual cycle.
FOM value near unity implies that the liquefier is approaching an ideal system.

Unit 1: Cryogenic Properties of Air

 Joule-Thomson Expansion
Most practical refrigeration and liquefaction systems obtain a reduction
in temperature with the aid of:
- an expansion valve (Joule-Thomson valve),
- an expansion engine,
- or a combination of the two devices.
In the case of the expansion valve, the flow within the valve is irreversible as well as
non-isenthalpic. However, the inlet and outlet conditions have the same enthalpy.
The change in temperature of a fluid obtained with an isenthalpic change in pressure
is represented by the Joule-Thomson (JT) coefficient, defined as
𝜇𝐽𝑇 = 𝜕𝑇ൗ𝜕𝑝
𝐻
or the slope of isenthalpic lines on a pressure-temperature
diagram.
On such a diagram the isenthalps go through a maximum
identified as the inversion curve for a fluid.
The JT coefficient is zero along the inversion curve, positive
when an expansion through the valve results in a decrease in
temperature, and negative when an expansion through the
valve results in an increase in temperature.
Unit 1: Cryogenic Properties of Air
 Simple Linde-Hampson Cycle

Simple Linde cycle used as a Simple Linde cycle used as a

refrigerator Liquefier

Unit 1: Cryogenic Properties of Air

 Simple Linde-Hampson Cycle
One of the thermodynamic process to obtain cryogenic
temperatures is the simple Linde cycle.
In the ideal process, the gaseous refrigerant is compressed
isothermally at ambient temperature, rejecting heat to a
coolant. The compressed refrigerant is cooled before it
reaches the throttling valve in a heat exchanger by the
stream returning to the compressor intake. Joule Thomson
cooling upon expansion further reduces the temperature
until, in the steady state, a portion of the refrigerant under
appropriate conditions is liquefied.
For a refrigerator, the unliquefied fraction and the vapor
formed by liquid evaporation from the absorbed heat, Q,
are warmed in the heat exchanger as they are returned to
the compressor intake.
Application of an energy balance to the refrigeration cycle
without the compressor and assuming reversibility in all
process steps except across the expansion valve reveals
that the work of compression per unit mass compressed is
just
−𝑊/ ሶ 𝑚ሶ = 𝑇1 𝑠1 − 𝑠2 − ℎ1 − ℎ2
Unit 1: Cryogenic Properties of Air
 Simple Linde-Hampson Cycle
The refrigeration duty is given by
𝑄ሶ = 𝑚ሶ 𝑇4 𝑠𝑔 − 𝑠4 = 𝑚ሶ ℎ𝑔 − ℎ4
However, assuming no heat inleaks to the
refrigeration system as well as negligible kinetic
and potential energy changes in the fluid, one can
show by an energy balance around the heat
exchanger, expansion valve, and liquid reservoir
that the refrigeration duty is also equivalent to
𝑄ሶ = 𝑚ሶ ℎ1 − ℎ2
Thus, the coefficient of performance) for the ideal
simple Linde refrigerator is given by
𝑄ሶ
𝑚ሶ
𝐶𝑂𝑃 = 𝑊ሶ
𝑚ሶ

= ℎ1 − ℎ2 /[𝑇1 𝑠1 − 𝑠2 − ℎ1 − ℎ2 ]
Unit 1: Cryogenic Properties of Air
 Simple Linde-Hampson Cycle
The simple Linde cycle may also be used as a liquefier
for fluids that have an inversion temperature that is
above ambient temperature. Under such circumstances,
the refrigeration duty, 𝑄,ሶ is replaced by a draw-off
stream of mass 𝑚ሶ 𝑓 representing the liquefied mass of
fluid that is continuously withdrawn from the reservoir.
Note that under these conditions, only the unliquefied
mass of fluid is warmed in the counter-current heat
exchanger and returned to the compressor.
An energy balance around the heat exchanger, expansion valve, and liquid reservoir
now results in
𝑚ℎ
ሶ 2 = 𝑚ሶ − 𝑚ሶ 𝑓 ℎ1 + 𝑚ሶ 𝑓 ℎ𝑓
because of the unbalanced flow in the liquefaction system. If we define the fraction
liquefied in a liquefier as y= 𝑚ሶ 𝑓 /𝑚,ሶ then we can solve above Eq. for the fraction
liquefied in a simple Linde cycle as
𝑦 = ℎ1 − ℎ2 / ℎ1 − ℎ𝑓
where hf is the specific enthalpy of the liquid being withdrawn.
Liquefaction is maximized when the difference between ℎ1 and ℎ2 is maximized.

Unit 1: Cryogenic Properties of Air

 Simple Linde-Hampson Cycle
Since ℎ1 and ℎ𝑓 are generally fixed, this means that
ℎ2 must be minimized. Mathematically, since 𝑇1 and
𝑇2 , this means that
𝜕ℎൗ
𝜕𝑝 𝑇= 𝑇 = 0
1
This is equivalent to saying that the high pressure p2
which minimizes h2 is the pressure at which the
Joule-Thomson coefficient is zero for a temperature
of 𝑇1 .
In other words, for maximum liquid yield, point 2 on
Fig. should occur at the intersection of 𝑇1 and the
inversion curve of the fluid at pressure p2.
To account for the at inleak, qL, into the system, the
relation in Eq. needs to be modified to
𝑦 = ℎ1 − ℎ2 − 𝑞𝐿 / ℎ1 − ℎ𝑓
with a resultant decrease in the fraction liquefied.

Unit 1: Cryogenic Properties of Air

 Simple Linde-Hampson Cycle
The figure of merit for this liquefier, then becomes
𝑇1 𝑠1 − 𝑠𝑓 − ℎ1 − ℎ𝑓 ℎ1 − ℎ2
𝐹𝑂𝑀 =
𝑇1 𝑠1 − 𝑠2 − ℎ1 − ℎ2 ℎ1 − ℎ𝑓

Unit 1: Cryogenic Properties of Air

 Problem:
A simple Linde liquefaction system operates between 290 K and 71.9 K and uses
nitrogen as the working fluid. The gas is isothermally and reversibly compressed
to 10.1 MPa. The low pressure corresponds to the saturation pressure of liquid
nitrogen at 71.9 K (0.05 MPa). Assuming ideal heat exchangers and no heat
inleak to the system, what is the liquid yield and FOM for this liquefier?
If the simple Linde liquefier had been utilized as a refrigerator, determine the
refrigeration effect, coefficient of performance, and figure of merit for the
system.
Properties of nitrogen from the temperature-entropy diagram are as follows:
h1(0.05 MPa, 290 K) = 452 kJ/kg
s1(0.05 MPa, 290 K) = 4.59 kJ/kg-K
h2(10.1 MPa, 290 K) = 432 kJ/kg
s2(10.1 MPa, 290 K) = 2.95 kJ/kg-K
hf(0.05 MPa, 71.9 K) = 18 kJ/kg
sf(0.05 MPa, 71.9 K) = 0.27 kJ/kg-K

Unit 1: Cryogenic Properties of Air