Refrigeration and Liquefaction

Lecturer : Dr. Bregas S T Sembodo, ST, MT

Universitas Sebelas Maret

Chemical Engineering Departement
 Refrigeration and liquefaction
• Refrigeration - Cooling of an object and maintenance
of its temperature below that of surroundings
• 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.
 High High
Temperature, TH Temperature, TH

QH QH

REFRIGERATOR Heat Engine W

W

QC QC

Low Temperature, Low Temperature,

TC TC
Refrigerator Heat Engine (e.g. Steam Power Plant)
 The Carnot Refrigerator
• The ideal refrigerator, like the ideal heat engine,
operates on a Carnot cycle, consisting of two
isothermal steps in which heat |QC| is absorbed at
the lower temperature TC and heat |QH| is rejected
at the higher temperature TH and two adiabatic
steps.
• The coefficient of performance:

heat absorbed at the lower temperatur e | QC | | QC | TC

   
net work W | QH |  | QC | TH  TC
 The vapor-compression cycle
• 1→2: liquid (absorb heat) evaporating at constant
pressure
• 2→3: isentropic compression to a higher pressure
• 3→4: cooled and condensed with rejection of heat
at a higher temperature level
• 4→1: expansion throttling process
Condenser

Fig 9.1

Evaporator
On the basis of a unit mass of fluid
The heat absorbed in the evaporator: | QC | H 2  H1
| QC | H 2  H1
The heat rejected in the condenser: | QH | H 3  H 4  
W H3  H 2
The work of compression: W  H3  H 2

| Q C |
Define the rate of circulation of refrigerant: m 
H 2  H1
A refrigerated space is maintained at -20oC and cooling water is available at 21°C.
Refrigeration capacity is 120.000 kJ/hr. The evaporator and condenser are of
sufficient size that a 5°C minimum-temperature difference for heat transfer can be
realized in each. The refrigerant is 1,1,1,2-tetrafluoreothane (HFC – 134a), for which
data are given in Table 9.1 and Fig F.2 (App. F). (1) what is the value of ω for a
Carnot refrigerator? (2) Calculate ω and ṁ for the vapor-compression cycle of Fig 9.1
if the compressor efficiency is 0.80.

(1) Temperature difference = 5oC

The evaporator temperature is : TC = -20oC - 5oC = -25oC = 248.15 K
The condenser temperature is : TH = 21oC + 5oC = 26oC =

TC 248.15
For a Carnot refrigerator:    4.87
TH  TC (299.15)  (248.15)
 kJ kJ
(2) At -25°C, HFC – 134a vaporizes at 1.064 bar: H 2  383.45 S 2  1.746
kg kg .K

kJ
At 26°C, HFC – 134a condenses at 6.854 bar H 4  235.97  H1
kg

Compression step is reversible and adiabatic (isentropic) from 2 to 3’:

kJ at 6.854 bar kJ
S3  S 2  1.746 H 3  421.97
kg .K kg
kJ kJ
 H S  H 3  H 2  38.52 H 3  H 2   H  S /   48.15
kg kg

H2  H4 | QC | 120000 kg
  3.06 m   814
H3  H 2 H 2  H1 383.45  235.97 hr
 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. CCl3F, CCl2F2) 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., CHCl2CF3, CF3CH2F).
Two-state cascade: (with TH 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.

Condenser at TH

Cycle 2

Fig 9.3

Cycle 1

Evaporator at TC
 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.
 |QH|
Heat discarded to
Heat added from surroundings at TS
source at TH
3
4
Condenser
Regenerator

Heat
exchanger
2

Evaporator 1
Absorber

Pump Heat absorbed for

Heat discarded to
|QC| refrigeration at TC
surroundings at TS

|W | T TH
The heat required for the production of work:   | Q |  1  T | QH || W |
S

H H TH  TS

TS  TC
The work required by a Carnot refrigerator: W | QC |
TC

TH TS  TC
| QH || QC |
TH  TS TC
 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.
Summer Evaporator

Condenser

Winter
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?

The minimum power requirements are provided by a Carnot heat pump:

For winter heating, the heat absorbed in the ground coils:

TC  10  273.15  kJ
| QC || QH |  30   28.02
TH  30  273.15  s

The power requirement: W | Q |  | Q | 30  28.02  1.98 kJ

H C
s

For summer cooling, the house coils are at the lower temperature TC :
The power requirement: TH  TC (25  273.15)  (5  273.15) kJ
W | QC |  60  4.13
TC 5  273.15 s
 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
 Fig 9.5

• 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
 The Linde liquefaction process
• Depends solely on throttling expansion:
– Compression – cooling to ambient temperature (even
further by refrigeration) – throttling and liquefaction.

Exchanger
Throttle
cooler Valve

Win Compressor

Separator

Gas feed Liquid

 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.

Exchanger Exchanger

cooler Throttle
Valve
Wout
Win Compressor

Separator

Gas feed Liquid

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 (at 300 K and 60 bar )
kg
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 on the right of the dashed vertical line: m 9 H 9  m 15H15  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

  H5 

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  H 4 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  14  m
m 4 m
9

1 z
H7  H5  H14  H12   719.8 kJ T  197.6 K
1 x kg 7 (at 60 bar )

Eventually approaching the saturation temperature in the separator

x  T7 
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  z  0.0541
H 9  H15
5.41 % of the methane entering the throttle valve emerges as liquid!
H 7  H 4  (1  z )H15  H10   769.2
kJ
kg T7  206.6 K (at 60 bar )