Chapter 9 Refrigeration and Liquefaction

• Application
– Air conditioning of buildings, transportation, and preservation
of foods and beverages
– Manufacture of ice
– Dehydration of gases
– Low-temperature reactions
– Separation of volatile hydrocarbons
– Continuous absorption of heat at a low temperature level.
Carnot Refrigerator
The ideal refrigerator, operating on a Carnot cycle:
Two isothermal steps: heat |QC| is absorbed at low temperature TC, rejected |
QH| at the higher temperature TH
Two adiabatic steps: expansion and compression
 Coefficient of performance:

For ideal (Carnot) cycle,

The coefficient of performance:

It gives maximum possible coefficient for any refrigerator

operating between TH and TC

For a refrigeration at HC = 5 oC and TH = 30 oC

 The vapor-compression cycle (Rankine refrigeration cycle)

or boiler

•1→2: liquid (absorb heat) evaporating at constant pressure (so constant T)

•2→3: isentropic (reversible and adiabatic) compression to a higher pressure
•3→4: cooled and condensed with rejection of heat at a higher temperature level
•4→1: expansion throttling process
 Rankine refrigeration cycle

or boiler

On the basis of a unit mass of fluid

The heat absorbed in the evaporator (constant P):
The heat rejected in the condenser (constant P):
The work of compression (Eq. (2.32)):

Define the rate of circulation of refrigerant:

P-H diagram is more commonly used than T-S diagram
because they show directly the required enthalpy.
C
ln P
Constant S

4
liquid 3
gas

1 2

H
Example 9.1
A refrigerated space is maintained at 10°F and cooling water is available at 70°F.
Refrigeration capacity is 120000 Btu/hr. The evaporator and condenser are of
sufficient size that a 10°F minimum-temperature difference for heat transfer can be
realized in each. The refrigerant is tetrafluoreothane (HFC – 134a), for which data
are given in Table 9.1 and Fig G.2 (App. G). (1) what is the value of ω for a Carnot
refrigerator? (2) Calculate ω and m  for the vapor-compression cycle of Fig 9.1 if the
compressor efficiency is 0.80.
Condensation T (80oF) is 10 oF
higher than cooling water T
Temperature of the
T 3 cooling water, Tcw
3’
4
TH and TC
70oF
should be zero
10oF for maximum
performance
1 2

Temperature of the S
refrigerated region, Tref Evaporation T (0 oF) is 10 oF lower than
refrigerator T
(1) For a Carnot refrigerator: TC 0  459.67
   5.75
TH  TC (80  459.67)  (0  459.67)
Note: K = (oF + 459.67)x5/9
(b) For irreversible refrigerator, Carnot engine cannot be used:
TC
We cannot calculate coefficient of performance using  
H 2  H1
TH  TC
We need to use 
H3  H2

4
3’ 3

2
1
 Data from Table 9.1:
At 0°F, HFC – 134a vaporizes at 21.162 (psia) (using Hv in Table 9.1):
Btu Btu
H 2  103.015 S 2  0.22525
lbm lbm R

At 80°F, HFC – 134a condenses at 101.37 (psia) (using Hl)

Btu
H 4  37.978
lbm
 The choice of refrigerant
• Dependence?
– The coefficient of performance of a Carnot refrigerator is
independent of the refrigerant.
– In practical refrigerators, vapor-compression cycle causes the
coefficient of performance to dependent to some extent on the
refrigerant because of irreversibility.
• Other factors:
– toxicity, flammability, cost, corrosion properties, vapor pressure in
relation to temperature, etc.

Comments on using refrigerator as an air conditioner for cooling room temperature

The room temperature increases because

• Both QH and QC are inside the room, no net heat is pumped out the
room. The work done by the surrounding will add heat to the
room.
• the second thermodynamics irreversible machine cannot reach
100% efficiency.
• Two requirements:
– The vapor pressure of the refrigerant at the evaporator temperature should be
greater than atmospheric pressure to avoid air leaking.
– The vapor pressure at the condenser temperature should not be too high,
because of the initial cost and operating expense of high-pressure equipment.
• Refrigerants
– Ammonia, methyl chloride, carbon dioxide, propane and other hydrocarbons
– Halogenated hydrocarbons
• common in 1930s (e.g. CCl3F, CCl2F2), stable molecules causing severe ozone depletion
• replacements are certain hydrochlorofluorocarbons, less than fully halogenated
hydrocarbons, and hydrofluorocarbons which contains no chlorine (e.g., CHCl 2CF3
(dichlorotrifluoroethane) CF3CH2F (tetrafluoroethane).
To reduce the temperature of the refrigerator, two-cycles operation is accepted

The heat absorbed in the interchanger by the refrigerant of the higher-temperature

cycle 2 serves to condense the refrigerant in the lower temperature cycle 1.

Example: A two stage cascade refrigeration

system works between TC of 210K and TH of
305K. Intermediate temperature are T’C = 255K
and T’H = 260K. Assume both refrigerators absorb
same amount of heat (QC = Qc’)
1. determine  for the real cascade
2. determine  if only one Carnot refrigerator
operates between TC and TH and absorbs the
same amount of heat QC from cold reservoir.
3. Which refrigerator device needs more work?
 Absorption refrigeration
In vapor-compression refrigeration the work of compression is usually supplied by
an electric motor

Absorption refrigeration: The direct

use of heat as the energy source for
refrigeration (not from an electric
motor).

The most commonly used absorption-

refrigeration system operates with
water as the refrigerant and a lithium
bromide solution as the absorbent.

Low-pressure steam is the usual

source of heat for the regenerator.

Involve 4 heat transfer points (Evaporator, absorber, regenerator and condenser

Two shaft work requiring devices (pump and Condenser)
Equals to a Carnot heat engine

Equals to a Carnot heat engine

 The heat pump
• Pump from a low-temperature source to a high-
temperature sink by expending work
• For heating houses in winter:
– Refrigerant is heated and evaporates in coils placed
underground or in the outside air; vapor compression is
followed by condensation, heat being transferred to air
or water, which is used to heat the building.
• Cooling houses in summer:
– The flow of refrigerant is reversed, and heat is absorbed
from the building and rejected through underground
coils or to the outside air.
High-P Liq. Condenser

High-P vap.

Low-P
Vap.
Evaporator
or boiler

High-P Liq. Low-P

Liq. + Vap.
Example 9.2 A house has a winter heating requirement of 30 kJ/s and a summer
cooling requirement of 60 kJ/s. Consider a heat-pump installation to maintain the
house temperature at 20°C in winter and 25°C in summer. This requires circulation
of the refrigerant through interior exchanger coils at 30°C in winter and 5°C in
summer. Underground coils provide the heat source in winter and the heat sink in
summer. For a year-round ground temperature of 15°C, the heat-transfer
characteristics of the coils necessitate refrigerant temperatures of 10°C in winter
and 25°C in summer. What are the minimum power requirements for winter heating
and summer cooling?
Winter Summer

20oC 25oC
QH=30kJ/s QC=60kJ/s
interior exchanger interior exchanger coils
T=30oC T=5oC
Condenser
15oC 15oC
Condenser
Compressor Expansion Compressor
Expansion
and evaporation and evaporation 25oC
10oC

QC
QH
The above example indicates that the heat pump can pump 30 kJ/s heat from cold
reservoir to hot reservoir by providing only 1.98kJ/s shaft work. From this result
one designed a device as below:
1. Using a heat pump to transfer large amount of heat (QH) from cold reservoir (TC) to
hot reservoir (TH) by providing small amount of shaft work (W1)
2. Building a heat engine between TH and TC. The heat engine absorbs the same
amount of heat that heat pump released to hot reservoir (QH), then provide shaft
work W2.
This designer believes by this way, he can continually provide extra work to
surrounding. Give your comments about this designer’s invention.
TH TH
QH QH
W1 W2
QC1 QC2

TC TC
Heat pump Heat engine
 Liquefaction processes
• Common use for:
– Liquid propane
– Liquid oxygen
– Liquid natural gas for ocean transport
– Liquid nitrogen for low temperature refrigeration
– Gas mixture are liquefied for separation
• By cooling gas to a two-phase region:
– By heat exchanger at constant pressure
– By an expansion process from which work is obtained
– By a throttling process
• By heat exchanger at constant pressure (1)
– Requires a heat sink at temperature lower than that to which the gas is
cooled
– Most commonly used to precool a gas prior to its liquefaction by
other two methods

• By an (isentropic) expansion process (2).

– It eventually can reach the two phase region
• By a throttling process (3)
– The throttling does not result in liquefaction unless the initial
state is at a high enough pressure and low enough Cooling processes on a TS diagram
temperature prior to throttling - path 3’:
– A and A’ usually have the same temperature but A’ has
lower pressure
– The change of state from A to A’: compression of the gas to
B, followed by constant-pressure cooling
– Then, throttle to 3’ results in the formation of liquid
– Commonly used for small-scale commercial liquefaction
plants
 The Linde liquefaction process

• Depends solely on
throttling
expansion
– Compression –
cooling to ambient
temperature (even
further by
refrigeration) –
throttling and
liquefaction.
 The Claude liquefaction process
• Replace the throttle valve by an expander:
– Gas – expander – saturated or slightly superheated vapor – cooled and
throttled to produce liquefaction (as in the Linde process) – unliquefied
portion mixes with the expander exhaust and returns for recycle.

Purpose: Reduce
temperature so it can
be used to cool the
gas through
exchanger II.
In this equation z is the fraction of the stream entering the heat-
exchanger system that is liquefied, and x is the fraction of this
stream that is drawn off between the heat exchangers and passed
through the expander. This latter quantity (x) is a design variable,
and must be specified before Eq. (9.7) can be solved for z. Note
that the Linde process results when x = 0, and in this event Eq.
(9.7) reduces to.
Example 9.3 Natural gas, assumed here to be pure methane, is liquefied in a
Claude process. Compression is to 60 bar and precooling is to 300 K. The
expander and throttle exhaust to a pressure of 1 bar. Recycle methane at this
pressure leaves the exchanger system at 295 K. Assume no heat leaks into the
system from the surroundings, an expander efficiency of 75%, and an expander
exhaust of saturated vapor. For a draw-off to the expander of 25% of the methane
entering the exchanger system, what fraction of the methane is liquefied, and
what is the temperature of the high-pressure steam entering the throttle valve?

kJ
For superheated methane: H 4  1140.0 kg
(at 300 K and 60 bar )

kJ
H15  1188 .9 (at 295 K and 1 bar )
kg
kJ
For saturated liquid: H 9  285.4 (T sat  111 .5 K and 1 bar )
kg
kJ kJ
For saturated vapor: H12  796.9 , S12  9.521 (T sat  111 .5 K and 1 bar )
kg kg  K
 An energy balance: m 9 H 9  m 15 H15  m 4 H 4  W out

The expander operates adiabatically: W out  m 12 ( H12  H 5 ) z  m 9 / m 4

A mass balance: m 15  m 4  m 9 x  m 12 / m 4

x H12  H 5   H 4  H15
z
H 9  H15

The equation defining expander efficiency: H  H12  H 5    H  S    H12  H 5 

Guess T5 → H5, S5 → isentropic expansion → H’12 → H12 → check if satisfied?

kJ
T5  253.6 K , H 5  1009.8 (at 60 bar )
kg

x H12  H 5   H 4  H15 0.25(796.9  1009.8)  1140.0  1188.9

z   0.113
H 9  H15 285.4  1188.9

11.3 % of the methane entering the exchanger system is liquefied!

An energy balance on the exchanger I: m 4 ( H 5  H 4 )  m 15 ( H15  H14 )  0
A mass balance: m 15  m 4  m 9 z  m 9 / m 4

H5  H4 1009.8  1140 .0 kJ
H14   H15   1188 .9  1042.1
1 z 1  0.113 kg T14  227.2 K (at 60 bar )

An energy balance on the exchanger II: m 7 ( H 7  H 5 )  m 14 ( H14  H12 )  0

A mass balance: m 7  m 4  m 12 m 14  m 4  m 9

1 z
H7  H5   H14  H12   719.8 kJ T  197.6 K (at 60 bar )
1 x kg 7
Eventually approaching the saturation temperature in the
x  T7 
separator and requiring an exchanger of infinite area! (i.e., cost
increases)
x H12  H 5   H 4  H15
For the Linde system, x = 0: z  H 9  H15
z  0.0541

5.41 % of the methane entering the throttle valve emerges as liquid!

kJ
H 7  H 4  (1  z ) H15  H10   769.2
kg T7  206.6 K (at 60 bar )