50

CHAPTER 4

REFRIGERANT SELECTION AND EXERGY ANALYSIS

4.1 REFRIGERANT SELECTION FACTORS

Refrigerant selection procedure for vapour compression system is

quite easy and not concerned with the environment where the high pressure
and high temperature refrigerant rejects the heat to the environment whereas
the low pressure and low temperature refrigerant absorbs heat from the
evaporator with not much loss at other points and is concerned only during
the leak or ejection of refrigerant to the environment. Table 4.1 explains the
general procedure and factors which govern the selection of refrigerants for
three stage ARC system.

Table 4.1 Selection criteria for three stage ARC refrigerant mixture

Sl.No Characteristics Comments/Concerns

1 Physical interaction between
refrigerants and other
components like lubricating oil
2 Freezing [or] melting point
3 Boiling point separation
4 Molecular mass
The refrigerants are strictly Zeotropic
in nature. They should not form
azeotropic mixture during operation.
Sufficiently low to avoid plugging as
well as critical temperature and
pressure are effectively low and high
for improved system performance
during operation.
Excellent during separation or
fractionation.
Less enough to get a good pressure
drop during expansion and good
enough to avoid pressure drops
through the pressure lines.
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Table 4.1 (Continued)

5 Molar latent heat High enough to get the improved heat

6 Lubricant miscibility with
higher boiling components
7 Flammability of individual
component and mixture
8 Stability
9 Toxicity
10 Cost and availability
11 Ozone depletion potential
12 Global warming potential
exchanger effectiveness and system
efficiency.
Refrigerants should not be miscible in oil
or vice-versa to completely separate the oil
from circulation in the system and manage
it completely to lubricate the compressor.
The quantity of refrigerant involved should
be less enough to have the personnel and
equipment safety during operation.
System should be durable for long term
working condition.
Refrigerants selected should not be toxic to
ensure personnel safety.
Refrigerants available should be cost
effective and readily available and
serviceable as well.
ODP of refrigerants should be
approximately Zero.
GWP of refrigerants should be
approximately Zero.

4.2 REFRIGERANT SELECTION, REASONS AND

RECOMMENDATIONS FOR THREE STAGE ARC
SYSTEM

Even though the general procedure and factors in selection of

refrigerants for ARC and simple vapour compression refrigeration system
were discussed in the last topic it is very essential to discuss the reasons and
recommendations of selection of refrigerants for all three stages of the three
stage ARC system. Table 4.2 lists out few of the refrigerants considered in
selection of refrigerant mixtures those have Zero ODP and very less value of
GWP in this study.
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Table 4.2 List of refrigerants considered, reasons and recommendations

for refrigerant selection of three stage ARC system

Sl.No Refrigerant Reasons and Recommendations

1 R1270 R1270 was considered for stage 1 as the first
[Propelene] refrigerant because the boiling temperatures at
high and low operating pressure were 48.67 oC &
-31.54 oC. The boiling temperature at low
pressure of first refrigerant was less than that of
boiling temperature at high pressure of second
refrigerants considered [R170 & R23]. The Mean
Effective Temperature Difference was also good
[Good hin, hout on both sides of the Cascade
condensers]. As it is a hydrocarbon the value of
GWP was very low and it has Zero ODP.
2 R290 R290 was considered for stage 1 as the first
[Propane] refrigerant because the boiling temperatures at
high and low operating pressure were 57.27 oC &
-25.43 oC. The boiling temperature at low
pressure of first refrigerant was less than that of
boiling temperature at high pressure of second
refrigerants considered [R170 & R23]. The Mean
Effective Temperature Difference was also good
[Good hin, hout on both sides of the Cascade
condensers]. As it is a hydrocarbon the value of
GWP was very low and it has Zero ODP.
3 R404A R404A was considered for stage 1 as the first
[Azeotropic refrigerant because the boiling temperatures at
Mixture] high and low operating pressure were 43.67 oC &
-31.23 oC. The boiling temperature at low
pressure of first refrigerant was less than that of
boiling temperature at high pressure of second
refrigerants considered [R170 & R23]. The Mean
Effective Temperature Difference was also good
[Good hin, hout on both sides of the Cascade
condensers]. As it is the mixture of
hydrofluorocarbon the value of GWP was very
low and it has Zero ODP.
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Table 4.2 (Continued)

4 R170 [Ethane] R170 was considered for stage 2 as second

refrigerant because the boiling temperatures at
high and low operating pressure were -7.156 oC
& -74.97 oC. The boiling temperature at high
pressure was well above the boiling temperature
of first refrigerant [R1270, R290 and R404A] at
low pressure. The boiling temperature at low
pressure was well below the boiling temperature
of third refrigerant [R14] considered at high
pressure. As it is a hydrocarbon the value of
GWP was very low and it has Zero ODP.
5 R23 R23 was considered for stage 2 as second
[Trifluoromethane refrigerant because the boiling temperatures at
[or] Fluoroform] high and low operating pressure were -8.307 oC
& -69.49 oC. The boiling temperature at high
pressure was well above the boiling temperature
of first refrigerant [R1270, R290 and R404A] at
low pressure. The boiling temperature at low
pressure was well below the boiling temperature
of third refrigerant [R14] considered at high
pressure. As it is a hydrofluorocarbon the value
of GWP was very low and it has Zero ODP.
6 R14 R14 was considered for stage 3 as third
[Tetrafluoro refrigerant because the boiling temperatures at
-methane] high and low operating pressure were -65.87 oC
& -117.6 oC. The boiling temperature at high
pressure of this third refrigerant was less than that
of the boiling temperature at low pressure of
second refrigerant considered [R170 & R23]. As
it is a hydrofluorocarbon the value of GWP was
very low and it has Zero ODP.
7 R50 Even though R50 have zero ODP & lesser GWP,
[Methane] it was not considered for operation because the
boiling temperatures at high and low operating
pressure were -89 oC & -180 oC and the
temperature overlap was not getting matched
between the considered refrigerants.
 54

Table 4.2 (Continued)

8 R32 Even though R32 have lesser values of ODP &

[Difluoromethane GWP, it was not considered for stage 1. As the
(or) Methylene boiling temperatures at high and low pressure were
Fluoride] 31.43 oC & -37.32 oC, R32 may not get completely
condensed by air cooled condenser during
operation at atmospheric temperature and higher
operating pressure.
9 R125 Even though R125 have lesser values of ODP &
[Pentafluoro GWP, it was not considered for stage 1. As the
-ethane] boiling temperatures at high and low pressure were
39.88 oC & -33.21 oC, R125 may not get
completely condensed by air cooled condenser
during operation at atmospheric temperature and
higher operating pressure.
10 R134a [1,1,1,2- R134a was not considered for stage 1. As the
tetrafluoroethane] boiling temperatures at high and low pressure were
67.48 oC & -10.08 oC, R134a will be in the form of
liquid during compression and will damage the
compressor.
11 R152a R152a was not considered for stage 1. As the
[Difluoroethane] boiling temperatures at high and low pressure were
72.65 oC & -7.492 oC, R152a will be in the form of
liquid during compression, will damage the
compressor and have very less temperature glide
between the second refrigerants considered.
12 R600 R600 was not considered for Stage 1. As the
[n-Butane] boiling temperatures at high and low pressure were
114.4 oC & 18.78 oC, R600 will be in the form of
liquid during compression, will damage the
compressor and have very less temperature glide
between the second refrigerants considered.
13 R600a R600a was not considered for Stage 1. As the
[Iso-Butane] boiling temperatures at high and low pressure were
100.4 oC & 7.111 oC, R600a will be in the form of
liquid during compression, will damage the
compressor and have very less temperature glide
between the second refrigerants considered.
14 R744 [Carbon Even though non-flammable, non-toxic with high
Dioxide(CO2)] critical pressure of 73.8 bar and boiling temperature
of -78.4 oC, its triple point (-56.6 oC)restricts the
use of CO2 as refrigerant in the case of applications
below -56.6 oC.
 55

4.3 NATURAL REFRIGERANT - [CO2]

The use of CO2 has disappeared around 1940’s with the

development of fluorocarbon even with the entire dominance of it as
refrigerant in the early 20th century. The use of CO2 was not there for about
half a century before Professor Gustav Lorentzen in the late 1980s proposed
to reconsider it. Non-flammability and non-toxicity as well as increased focus
on environmental issues of fluorocarbons created a strong interest in systems
using natural fluids as refrigerants.

4.3.1 Factors of Carbon Dioxide as Refrigerant

The most remarkable property of CO2 is the low critical

temperature of 31.1 oC. Vapour compression systems work close to and even
above the critical pressure of 73.8 bar with CO2 as refrigerant, operating at
normal ambient temperatures which gives the following advantage during
operation.

High-side pressure in a tanscritical system is determined by

refrigerant charge and not by saturation pressure because the
system use a tanscritical cycle that operates partly below and
partly above the critical pressure and heat is rejected at
supercritical pressure.

Delivers high compressor efficiency due to the fact that only

80-90% smaller compressor displacement is needed for the
capacity of the system designed due to the higher operating
pressure which is nearly around 70bar.
 56

Very useful in the case of heat recovery applications where

almost the heat rejection takes place not as a condenser
theory, instead it is nothing but cooling the refrigerant from
compressed condition (Gas cooler). Large refrigerant
temperature glide during heat rejection helps the heat transfer
process to be perfect and this contributes to high COP of the
system.

The interest and focus on reduction of climatic gas emissions has

lead the situation of phase out of HFC’s and directs the refrigeration
industries towards the use for natural refrigerants such as hydrocarbons,
ammonia and CO2. Developments in european countries has given ways and
means of CO2 as refrigerants in refrigeration systems which has resulted the
new technologies for higher COP, higher cooling and heating capacity with
better comfort and added possibilities of heat recovery well before a decade.

The justification for the return to the original natural refrigerants is

therefore great. These refrigerants are cheap, do not damage the environment
and are technically excellent in their range of application. Modern design
techniques and equipment have dramatically reduced the risks associated with
the use of these fluids and it only remains to demonstrate the industry that
these refrigerants can be safely and cost effectively applied in order to
achieve an extensive reduction in the use of fluorocarbons. The system should
withstand the very high operating pressure such as 75 to 100 bar with the
advantage of the refrigerant as such is very less in hazardous to nature and
does not cause any damage to the system in case of any fire compared with
HFC’s.

The system performance were excellent using CO2 as refrigerant

with reduced dimensions upto one sixth [1/6] or one eighth [1/8] of an
 57

ordinary refrigeration system which uses ammonia or fluorocarbon as

refrigerants. But the major drawbacks of CO2 are the low critical temperature
(31.1 °C) and the high operating pressures. These properties render CO2 less
useful as a refrigerant in a single stage system. Since these systems require
inefficient trans-critical operation, CO2 is best used as the low stage
refrigerant in a cascade system with the condensing temperature of CO2
remains sufficiently low giving superb efficiency with compact plant design
for the given refrigeration capacity.

Since CO2 changes directly from liquid to solid below its triple
point at -69.9 °F (-56.6 °C) at 61.5 psig (424 kPa), avoids the problem of
liquid leak. However CO2 is not economical to be used in ARC systems
especially below application temperatures of -56.6 C, because of the reasons
that it has the triple point of -56.6 °C even with the boiling temperature of
-78.4 °C and also higher operating pressures. Hence CO2 can be eliminated
from the possible refrigerant mixtures list, as this work deals on the low
temperature application around -90 °C.

4.4 SELECTION CRITERIA FOR REFRIGERANT MIXTURES

i. Temperature glide [boiling point difference between the

mixture components]

ii. Zero ODP and minimum GWP values

iii. Operating pressure range

iv. Zeotropic nature of mixture

v. Molecular mass

vi. Cost and availability

 58

The selection of refrigerant combinations is done based on

difference in boiling point, ODP, GWP, physical properties, operating
pressure range, suction pressure, delivery pressure and safety. As all of the
refrigerant components of the mixture were working at the same pressure
range, the selection becomes more important. Based on these criteria,
following refrigerant combinations were selected. They are

i. R290 / R170 / R14

ii. R290 / R23 / R14

iii. R404A / R 170 / R14

iv. R1270 / R170 / R14

4.5 PERFORMANCE ANALYSIS

4.5.1 Energy Analysis

In general first and second law of thermodynamics are used to

analyse the system performance. All forms of energy are considered to be
equivalent in an energy analysis, based on the first law of thermodynamics. In
this analysis loss of quality of energy is not taken into account. During the
process of heat rejection from the system to the surrounding at condenser
[higher temperature to lower temperature], the change of the quality of
thermal energy cannot be quantified or demonstrated and also it is a
continuous process and we consider the energy flow to be continuous in
nature.

4.5.2 Exergy Analysis

An exergy analysis or the quantification of system imperfection,

based on the first as well as the second law of thermodynamics shows that the
 59

system with near equilibrium state has the highest performance and being the
most efficient and effective system where there won’t be any heat loss to the
environment which cannot be retrieved or used back. An energy balance is
always closed as stated in the first law of thermodynamics. There can never
be an energy loss, only energy transfer to the environment in which case it is
useless. For pinpointing and quantifying the irreversibility an exergy analysis
has to be performed.

The exergy analysis being the complementary to the energy

analysis based on First law of thermodynamics cannot be replaced. This
exergy analysis and the concept of second law of thermodynamics has
invoked considerable interest in recent years due to the fact that its
application leads to a better understanding of the process of energy transfer
and helps to identify the thermodynamic losses with quantification.

Since the studies applying second law analysis for refrigeration

process does not take into account the quality of energy and assigns the
relationship between high quality and low quality energy process, it takes
considerable dominance over the energy analysis. Moreover, it results in
assigning efficiency values greater than unity for certain refrigeration process
and heat pump applications, thus departing from the efficiency concepts.
Second law of thermodynamic analysis takes in to account the quantity of
energy consumed and the quality of the energy conserved. This also permits
to identify the losses occurring in different components of the system and thus
has the prediction of thermodynamic efficiency for any application.

Exergy of a system denotes the maximum amount of work that can

be obtained when the system is allowed to come back to equilibrium with the
surroundings. The state of the surrounding is called ‘dead state’. This can be
measured in terms of the following two terms “thermo-mechanical
availability” and “chemical availability”.
 60

The term “thermo-mechanical availability” which is the difference

between energy levels of the system at operating condition and the system at
“restricted dead state” where the system is in thermal and mechanical
equilibrium with the surrounding and not permitted to mix or enter in to
chemical reaction with the surrounding from where the maximum amount of
work obtained during the reversal of the process.

The next term “chemical availability” is the level of work due to

concentration difference between the systems at “restricted dead state” and
surrounding at “absolute dead state” where the system is in thermal,
mechanical and chemical equilibrium with the surroundings.

It is important to note that chemical availability plays a dominant

role in exergy analysis in process involving mixtures of chemical substances
or in chemical reactions (e.g. combustion) and should not be ignored. Hence,
for vapour compression refrigeration process it is sufficient to consider only
the “thermo-mechanical equilibrium” and also is evident not to consider the
state of absolute dead state due to the fact that the refrigerant mixtures do not
react chemically within the system during the operation of three stage ARC
system.

4.5.3 Importance of Exergy Analysis

Exergy is the term not dealing with the conservation of energy law
but it is the quantity of high quality energy destroyed during any process due
to the irreversibility. As heat energy has lower exergy or quality of energy
compared with work, it is not possible to convert heat into work with 100%
efficiency [Perpetual Motion Machine is not Possible] but it is possible to
convert work into heat at 100% efficiency because of the fact that work has
higher exergy or quality of energy. Since the exergy analysis provide a better
view of the real efficiency of a process, it is very useful to find the unit
 61

operation where efficiency improvement are most wanted and useful, the
exergy analysis is more accurate and scientifically correct when compared to
an ordinary energy analysis.

Process designer or process engineer should perform an exergy

analysis to make all exergy losses visible in the process under study. The
method is very powerful when compared to two or more solutions in an
objective and quantitative manner. Exergy analysis is especially useful in the
design phase and during optimisation of new processes in terms of exact
location for improvement by giving the best clues where to start, namely at
the point where the largest exergy losses appear but not give direct answers
on how to improve the efficiency of the process.

4.6 CONCEPTS OF EXERGY ANALYSIS

The purpose of the exergy analysis is to find the temperature,

pressure, enthalpy and entropy at the different state points of the system. By
incorporating these parameters the energy balance in the cycle can be done
and also the exergy loss at the various components can be calculated. The
exergy loss at the various components can be calculated as follows. The
general exergy equation,

(v vo ) 2
e u uo po (v vo ) To ( s so ) g ( z zo )
2 (4.1)

Exergy at a given point can be calculated by

e h h0 T0 s s0 (4.2)

Exergy losses are calculated by making exergy balance for each

component of the system. Unlike energy balance where the inflow is equal to
 62

the outflow (when there is no energy generation or consumption), in exergy

balance due to reasons of irreversibility, the exergy inflow is always greater
than the exergy outflow and their difference gives the exergy loss. This
exergy loss has to be reduced to improve the thermodynamic efficiency of the
system.

Exergy balance can be stated as below

Exergy in = Exergy out + Irreversibility

For a steady state process having a mechanical input ‘w’ and one
fluid entering and leaving the system, the exergy loss can be written as:

e loss e1 w e2
(4.3)

where the changes in potential and kinetic energies are neglected. Exergy
losses occurring during a cycle can be calculated by the summation of all the
exergy losses of the components.

The useful energy at the evaporator is given by

Qe m RIII (h 15 h 14 ) (4.4)

And the compressor work or the input to the process is given by

wc m mix (h 2 h1 ) (m RI m RII m RIII ) (h 2 h1 ) (4.5)

The COP of the system is then calculated as

Q
COP
wc
(4.6)
 63

The overall exergic efficiency of the system is defined as the ratio

of exergy absorbed to the compressor work. It is given by

Exergy of cold produced

ex
Exergy of work input
(4.7)

The selection of an appropriate dead state is important as it is

explicitly used in calculating exergy. Hence changing the dead state will lead
to different exergy values. In the present analysis, the reference conditions
used are T0 = 301.3K, h = 200 kJ/kg, s = 1 kJ/kg K as prescribed by IIR.

4.7 EXERGY ANALYSIS PROCEDURE

The exergy analysis were done using the properties gathered as per
their state points using REFPROP-6 and following are the procedure followed
in this study for analysis.

i. The following refrigerant combinations were considered for

exergy analysis and study. The combinations were
a). R290 / R170 / R14, b). R290 / R23 / R14,
c). R404A / R 170 / R14, & d). R1270 / R170 / R14.

ii. Evaporator temperature was fixed as 153 K.

iii. The values obtained are plotted in a graph, which is discussed

in the result and discussion chapter.

4.7.1 Assumptions

The following assumptions were made for the study.

i. The compression process is polytropic with polytropic index

of 1.12
 64

ii. In the exit of the condenser the entire fraction of high boiling
refrigerant is condensed i.e. the high boiling refrigerant is
completely condensed.

iii. The vapour and liquid phases exist in equilibrium in the

separators I and II.

iv. Saturated liquid of refrigerant II is obtained at the exit of

cascade condenser I.

v. Saturated liquid of refrigerant III is obtained at the exit of

cascade condenser II.

vi. Only the latent heat of evaporation of the higher boiling

refrigerant (RI) is predominant.

vii. Heat gained by high boiling refrigerant (RI) is equal to the

heat lost by medium boiling refrigerant (RII) and Low boiling
refrigerant (RIII) at cascade condenser I and also heat gained
by medium boiling refrigerant (RII) is equal to heat lost by
low boiling refrigerant (RIII) at cascade condenser II. The
mass fraction is calculated based on this assumption.

viii. After mixing the initial composition is restored.