Advanced Thermodynamics

Note 8
Refrigeration and Liquefaction
Lecturer:
Refrigeration and liquefaction
Application
Air conditioning of buildings, transportation, and
preservation of foods and beverages
Manufacture of ice
Dehydration of gases
Petroleum industry include lubrication-oil purification
Low-temperature reactions
Separation of volatile hydrocarbons
Continuous absorption of heat at a low temperature
level, usually accomplished by evaporation of liquid
in a steady-state flow process.
The Carnot Refrigerator
The ideal refrigerator, like the ideal heat engine,
operates on a Carnot cycle, consisting of two
isothermal steps in which heat |Q
C
| is absorbed at
the lower temperature T
C
and heat |Q
H
| is rejected
at the higher temperature T
H
and two adiabatic
steps.
The coefficient of performance:
C H
C
C H
C C
T T
T
Q Q
Q
W
Q
work net
e temperatur lower the at absorbed heat

= =
| | | |
| | | |

The vapor-compression cycle

12: liquid (absorb heat)
evaporating at constant pressure
23: isentropic compression to
a higher pressure
34: cooled and condensed
with rejection of heat at a
higher temperature level
41: expansion throttling
process
Fig 9.1
On the basis of a unit mass of fluid
1 2
| | H H Q
C
=
The heat absorbed in the evaporator:
4 3
| | H H Q
H
=
The heat rejected in the condenser:
2 3
1 2
| |
H H
H H
W
Q
C

= =
2 3
H H W =
The work of compression:
Define the rate of circulation of refrigerant:
1 2
| |
H H
Q
m
C

Fig 9.2
A refrigerated space is maintained at 10F and cooling water is available at 70F.
Refrigeration capacity is 120000 Btu/hr. The evaporator and condenser are of
sufficient size that a 10F 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 for a Carnot
refrigerator? (2) Calculate and for the vapor-compression cycle of Fig 9.1 if the
compressor efficiency is 0.80.
m
(1) For a Carnot refrigerator: 75 . 5
) 67 . 459 0 ( ) 67 . 459 80 (
67 . 459 0
=
+ +
+
=

=
C H
C
T T
T

(2) At 0F, HFC 134a vaporizes at 21.162 (psia):

m
lb
Btu
H 015 . 103
2
=
R lb
Btu
S
m
22525 . 0
2
=
At 80F, HFC 134a condenses at 101.37 (psia): 1 4
978 . 37 H
lb
Btu
H
m
= =
R lb
Btu
S S
m
22525 . 0
2 3
= = '
Compression step is reversible and adiabatic (isentropic) from 2 to 3:
m
lb
Btu
H 117
3
= '
at 101.37 (psia)
)
m
S
lb
Btu
H H H 98 . 13
2 3
= ' = A )
m
S
lb
Btu
H H H 48 . 17 /
2 3
= A = g
72 . 3
2 3
4 2
=

=
H H
H H

hr
lb
H H
Q
m
m C
1845
978 . 37 015 . 103
120000 | |
4 2
=

The choice of refrigerant

Dependence?
The efficiency of a Carnot heat engine is independent
of the working medium of the engine.
The coefficient of performance of a Carnot refrigerator
is independent of the refrigerant.
Vapor-compression cycle cause the coefficient of
performance to dependent to some extent on the
refrigerant.
Other factors:
toxicity, flammability, cost, corrosion properties, vapor
pressure in relation to temperature, etc.
Two requirement:
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 unduly 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. CCl
3
F, CCl
2
F
2
) and now mostly end
stable molecules causing severe ozone depletion
replacements are certain hydrochlorofluorocarbons, less than
fully halogenated hydrocarbons, and hydrofluorocarbons
which contains no chlorine (e.g., CHCl
2
CF
3
, CF
3
CH
2
F).
Two-state cascade: (with T
H
fixed by the temperature of the surroundings, a lower
limit is placed on the temperature level of refrigeration).
The two cycles operate so that 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.
Fig 9.3
Absorption refrigeration
Absorption refrigeration: the direct use of heat as
the energy source for refrigeration (not from an
electric motor).
The essential difference between a vapor-compression
and an absorption refrigerator is in the different means
employed for compression.
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.
The work required by a Carnot refrigerator:
| |
C
C
C S
Q
T
T T
W

=
H
S
H
T
T
Q
W
= = 1
| |
| |
g
The heat required for the production of work:
S H
H
H
T T
T
W Q

= | | | |
Fig. 9.4
C
C S
S H
H
C H
T
T T
T T
T
Q Q

= | | | |
The heat pump
for heating houses in winter:
Refrigerant 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.
and cooling them 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.
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 20C in winter and 25C in summer. This requires circulation of the
refrigerant through interior exchanger coils at 30C in winter and 5C in summer.
Underground coils provide the heat source in winter and the heat sink in summer.
For a year-round ground temperature of 15C, the heat-transfer characteristics of the
coils necessitate refrigerant temperatures of 10C in winter and 25C in summer.
What are the minimum power requirements for winter heating and summer cooling?
The minimum power requirements are provided by a Carnot heat pump:
For winter heating, the heat absorbed in the ground coils:
s
kJ
T
T
Q Q
H
C
H C
02 . 28
15 . 273 30
15 . 273 10
30 | | | | =

'
+

'

+
+
= =
The power requirement:
s
kJ
Q Q W
C H
98 . 1 02 . 28 30 | | | | = = =
For summer cooling, the house coils are at the lower temperature T
C
:
The power requirement:
s
kJ
T
T T
Q W
C
C H
C
13 . 4
15 . 273 5
) 15 . 273 5 ( ) 15 . 273 25 (
60 | | =
+
+ +
=

=
Liquefaction processes
Common use for:
Liquid propane as a domestic foil
Liquid oxygen in rocket
Liquid natural gas for ocean transport
Liquid nitrogen for low temperature refrigeration
Gas mixture are liquefied for separation
Cooled to a temperature in the 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 - path 1
By an (isentropic) expansion
process - path 2
By a throttling process the
initial state must be at a high
enough pressure and low
enough temperature prior to
throttling - path 3:
The change of state from A to
A: compression of the gas to
B, followed by constant-
pressure cooling
Then, isentropic expansion 3
results in the formation of
liquid
Fig 9.5
The Linde liquefaction process
Depends solely on
throttling expansion:
Compression cooling to
ambient temperature (even
further by refrigeration)
throttling and liquefaction.
Fig 9.6
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.
Fig 9.7
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?
For superheated methane:
) 60 300 ( 0 . 1140
4
bar and K at
kg
kJ
H =
) 1 295 ( 9 . 1188
15
bar and K at
kg
kJ
H =
For saturated liquid:
) 1 5 . 111 ( 4 . 285
9
bar and K T
kg
kJ
H
sat
= =
For saturated vapor:
) 1 5 . 111 ( 521 . 9 , 9 . 796
12 12
bar and K T
K kg
kJ
S
kg
kJ
H
sat
=

= =
An energy balance on the right of the dashed vertical line:
out
W H m H m H m

= +
4 4 15 15 9 9
The expander operates adiabatically:
) (
5 12 12
H H m W
out
=

A mass balance:
9 4 15
m m m =
4 9
/ m m z
4 12
/ m m x
)
15 9
15 4 5 12
H H
H H H H x
z

+
=
The equation defining expander efficiency:
) )
5 12 5 12
H H H H H H
S
' = A = = A g g
Guess T
5
H
5
, S
5
isentropic expansion H
12
H
12
check if satisfied?
) 60 ( 8 . 1009 , 6 . 253
5 5
bar at
kg
kJ
H K T = =
)
113 . 0
9 . 1188 4 . 285
9 . 1188 0 . 1140 ) 8 . 1009 9 . 796 ( 25 . 0
15 9
15 4 5 12
=

+
=

+
=
H H
H H H H x
z
11.3 % of the methane entering the exchanger system is liquefied!
An energy balance on the exchanger I: 0 ) ( ) (
14 15 15 4 5 4
= + H H m H H m
A mass balance:
9 4 15
m m m =
4 9
/ m m z
kg
kJ
H
z
H H
H 1 . 1042 9 . 1188
113 . 0 1
0 . 1140 8 . 1009
1
15
4 5
14
= +

= +

=
) 60 ( 2 . 227
14
bar at K T =
An energy balance on the exchanger II: 0 ) ( ) (
12 14 14 5 7 7
= + H H m H H m
A mass balance:
12 4 7
m m m =
)
kg
kJ
H H
x
z
H H 8 . 719
1
1
12 14 5 7
=

=
) 60 ( 6 . 197
7
bar at K T =
9 4 14
m m m =
For the Linde system, x = 0:
)
15 9
15 4 5 12
H H
H H H H x
z

+
=
0541 . 0 = z
5.41 % of the methane entering the throttle valve emerges as liquid!
)
kg
kJ
H H z H H 2 . 769 ) 1 (
10 15 4 7
= =
) 60 ( 6 . 206
7
bar at K T =
+ T
7
T x
Eventually approaching the saturation temperature in the separator
and requiring an exchanger of infinite area! (i.e., cost increases)