Refrigerants For Vapour Compression Refrigeration Systems: G Venkatarathnam and S Srinivasa Murthy
Refrigerants For Vapour Compression Refrigeration Systems: G Venkatarathnam and S Srinivasa Murthy
Refrigerants For Vapour Compression Refrigeration Systems: G Venkatarathnam and S Srinivasa Murthy
Present day mankind depends very heavily on refrigeration (which (right) S Srinivasa Murthy’s
can be defined as artificial production of cold) for daily needs. interests are mixture based
refrigeration & heat pump
These cover a wide range of applications such as food processing,
systems, sorption cooling
preservation and transport, comfort cooling, commercial and systems, clean and renewable
industrial air conditioning, manufacturing, energy production, energy and heat & mass
health, recreation, etc. The first known machine to produce transfer in porous media.
Refrigeration Methods
Compression refrigeration
cycles Regenerative cycles
• Single effect
• Double effect
Thermoelectric
Refrigerators that operate with other types of energy input are Figure 1. Classification of
only used in niche applications. refrigeration methods based
on type of the variation of
This article deals with the refrigerants used in steady-state sys- pressure and flow rate in the
tems belonging to the broad category of vapour compression cycle during steady-state op-
eration.
refrigeration systems (VCRS) that operate using mechanical
power.
Figure 2. Schematic of a
simple vapour compression
refrigerator. The refrigerant
vapour is compressed in the
compressor (Process 1–2),
condensed in the condenser
(Process 2–3), expanded in a
throttling device (Process 3–
4) and evaporated in the
evaporator (Process 4–1).
Heat from the product to be
cooled is added at the evapo-
rator and rejected at the con-
Figures 3a and 3b are realized as follows:
denser to the ambient.
Process 1–2: Isentropic compression of the refrigerant.
Process 2–3: Constant pressure heat rejection1 in a heat ex-
changer termed as the condenser.
Process 3–4: Isenthalpic expansion2 of the refrigerant in an
1 The heat added in the evapora- orifice, valve or a capillary tube.
tor and the work supplied to the
Process 4–1: Constant pressure heat addition in a heat exchanger,
compressor are rejected in the
condenser.
usually termed as the evaporator.
2 Isenthalpic expansion process
is an irreversible process, and is Processes in a real refrigeration system will be slightly different
therefore normally shown in dot- from those shown in Figures 2 and 3 due to irreversibilities such
ted lines on a T-s (temperature– as pressure drop in heat exchangers caused by friction, accelera-
entropy) diagram.
tion of the refrigerant in the evaporator as the liquid turns into
vapour, pressure drop in the suction and discharge valves, non-
Figure 3. a) Clausius–Rank-
isentropic compression in the compressor, etc.
ine (1-2-3-4) and b) Lorenz–
Air and water are the two most commonly used external heat
Meutzner (1’-2’-3’-4’) cycles
operating with heat transfer
fluids that undergo a tempera-
ture change across the con-
denser/evaporator. The
Clausius–Rankine cycle is
used in refrigerators operat-
ing with single fluids and
azeotropic mixtures, and the
Lorenz–Meutzner cycle is
used in refrigerators operat-
ing with zeotropic mixtures.
The atmosphere is divided into layers defined by the distance above the surface of the earth as follows:
A proportion of the sun’s energy is emitted as ultraviolet (UV) radiation which can be divided into three types
according to the wave length:
It has been established that the short wavelength bands of the UV radiation are harmful to the life on earth in
many ways. It has also been established that a layer of the stratosphere, 20–40 km thick and rich in ozone, filters
out a major portion of this harmful UV radiation from reaching the earth’s surface. Chemically stable
chlorofluorocarbon (CFC) refrigerant molecules remain for a very long time in the atmosphere and can
therefore reach the ozone layer. In the stratospheric area an energetic UV photon strikes the CFC molecule.
The energy of the impact releases a chlorine atom, which is chemically very active and reacts with an ozone
molecule. Through this interaction, the ozone molecule is destroyed. This is a complicated chain reaction
leading to the ‘ozone hole’.
Health and environmental effects of ozone depletion can be multifarious. Because biological life on this planet
evolved only after the ozone shield developed, enormous potential for harm exists if the shield is damaged.
DNA, the genetic code present in all living cells is damaged by UV radiation, UVC being the most damaging.
A significant reduction in ozone in the upper atmosphere could result in long-time increase in skin cancer and
cataracts, and probably damage the human immune system. Environmental damage and the resulting
economic losses could be because of decreased yields of major agricultural crops, and reduced productivity
of phytoplankton with possible implications for the aquatic food chain, resulting in substantial losses at the
larval stage of many fish (e.g. anchovies, shrimps and crabs).
The extent of damage that a refrigerant can cause to the ozone layer is quantified by the Ozone Depletion
Potential (ODP), which is the ratio of impact caused by the substance on ozone to that caused by CFC 11.
History of Refrigerants
Period Refrigerants
1800–1900 Ethyl alcohol, methyl amine, ethyl amine, methyl chloride, ethyl chloride,
sulphur dioxide, carbon dioxide, ammonia
not survive, mainly due to their toxicity. Ammonia, however, Table 1. History of refrigerant
continues to be a refrigerant of choice for food freezing appli- usage.
cations even today in spite of its toxicity, mainly due to its
excellent thermodynamic and thermal properties. Carbon diox-
ide used in the early days of refrigeration is again being consid-
ered as a refrigerant in spite of its high operating pressures.
Hydrocarbons used in the early part of the last century were
quickly discontinued because of their flammability. However,
3 Global Warming Potential is the
hydrocarbons have made a successful comeback and are being
ratio of global warming impact
used extensively in small domestic refrigerators and freezers in caused by a substance to that
recent years. caused by CO2 of same mass in a
certain period of time.
The discovery of CFCs in the late twenties revolutionized the
refrigeration industry. Both CFCs and hydrochlorofluorocarbons
The discovery of CFCs
(HCFCs) are non-toxic, possess excellent thermodynamic prop-
in the late twenties
erties, and are non-flammable. Both CFCs and HCFCs domi-
revolutionized the
nated the refrigeration industry for nearly 70 years till the
refrigeration industry.
Montreal Protocol imposed a ban due to their contribution to
Both CFCs and HCFCs
ozone depletion. In the last two decades, hydrofluorocarbons
dominated the
(HFCs), which possess zero Ozone Depletion Potential (ODP),
refrigeration industry
have gradually replaced CFCs. Very recently, global warming
for nearly 70 years till
due to emission of various gases into the atmosphere has been
the Montreal Protocol
the issue being dealt with by the Kyoto Protocol (see Box 2).
imposed a ban due to
HFCs which have high Global Warming Potential3 (GWP) are
their contribution to
also being banned in spite of the fact that they are ozone
ozone depletion.
friendly. Hydrofluorooelifins (HFOs), which have very low
The earth and its atmosphere get heated as they continuously receive sun’s energy in the form of high frequency
radiation. A major part of this heat is returned as infrared radiation. Thus a delicate balance exists between the
energy received and that returned to the outer space. The temperature of the earth depends on this. Many gases
such as CO2, methane (CH4), nitrous oxide (N2O), various hydrocarbons, CFCs, HCFCs, HFCs, etc., are
released by mankind due to various agricultural and industrial activities. These gases, called ‘green-house
gases (GHG)’, act as a screen, blocking out part of the infrared radiation of the earth towards outer space. Water
vapour is also a powerful greenhouse gas but is not harmful as it is condensable and cannot build up in the
atmosphere. This is the reason that HFCs, even though are safe from the ozone depletion point of view, are
increasingly being blamed for contributing to the global warming.
In fact, man and animals emit significant amounts of GHGs due to their metabolic activity. Methane is a potent
greenhouse gas produced by ruminant animals, such as dairy cows. Animal agriculture is responsible for more
greenhouse gas (18%) than all of transportation (13%) according to a 2006 report of the UN-FAO. On Al
Gore’s website www.climatecrisis.org, he notes: “Eat less meat. Methane is the second most significant GHG,
and cattle are the greatest methane emitters. Their grassy diet and multiple stomachs cause them to produce
methane, which they exhale with every breath.” By being vegetarian, we grow plants which not only produce
food but also act as carbon sinks because they consume CO2.
CFCs (Chlorofluorocarbons)
R113 Trichlorotrifluroethane 320.73 238.16 487.3 34.4 0.9 5200
R11 Trichlorofluromethane 296.98 162.05 471.2 44.1 1 4000
R114 Dichlorotetrafluroethane 276.94 179.27 418.9 32.6 0.7 16600
R12 Dichlorodifluromethane 243.37 115.38 385.2 41.2 1 12200
R115 Chloropentafluroethane 233.83 167.05 353.1 31.5 0.6 39200
HCFCs(Hydrochlorofluorocarbons)
R141b Dichlorofluroethane 305.16 – 483.35 46.4 0.15 600
R123 Dichlrotrifluroethane 301.03 166.01 457.15 36.76 0.02 80
R22 Chlorodifluromethane 232.40 113.16 363.15 49.78 0.05 1480
HFCs (Hydrofluorocarbons)
R245fa Pentafluropropane 288.44 166.49 383.4 31.5 0 790
R134a Tetrafluroethane 247.00 176.55 374.25 40.67 0 1160
R507 Azeotrope - Blend 226.05 255.38 344.05 37.92 0 1400
R125 Pentafluroethane 224.59 170.01 339.25 36.2 0 3360
R32 Difluromethane 221.44 137.05 351.4 58.08 0 440
R23 Trifluromethane 191.10 118.16 298.75 48.37 0 24000
HFOs (Hydrofluorooellifins)
R1234yf 2,3,3,3-Tetrafluoropropene 244.15 220.00 367.85 33.82 0 4
FCs /PFCs (Fluorocarbons/Perfluorocarbons)
R218 Octofluropropane 241.66 113.16 344.95 26.8 0 9300
R14 Tetrafluromethane 145.22 89.27 227.65 37.43 0 6500
Hydrocarbons
R600 Butane 272.66 134.66 425.12 37.7 0 0
R290 Propane 231.07 85.49 369.83 42.1 0 0
R170 Ethane 184.35 90.38 305.32 48.5 0 0
R1150 Ethylene 169.44 104.27 282.34 50.3 0 0
R50 Methane 111.66 90.94 190.56 45.9 0 0
Inorganic Compounds
R718 Water 373.16 273.16 647.13 219.4 0 0
R717 Ammonia 239.83 195.44 405.65 113.0 0 0
R744 Carbon dioxide 194.72 216.55 304.21 73.9 0 1
R728 Nitrogen 77.38 63.16 126.2 33.9 0 0
R702n Hydrogen 20.38 13.99 33.19 13.2 0 0
R704 Helium 4.22 _ 5.2 2.3 0 0
HFEs (Hydrofluoroethers)
HFE-7100 Methoxynonafluorobutane 334.16 138.16 468.45 22.3 0 320
HFE-7200 Ethoxynonafluorobutane 349.16 135.16 482.0 19.8 0 55
HFE-7000 Methooxyheptafluropropane
307.16 150.38 438.15 24.8 0 400
Box 3
Figure 5(left). Vapour dome still significant. High volumetric capacities are associated with
of a typical refrigerant low values of . For maximum COP, an optimum value of
(HFC134a) with negative
exists. The heat capacity affects the performance of the vapour
slope of the saturated vapour
compression cycle primarily through its influence on the shape of
line.
the two-phase region or ‘vapour dome’ on the temperature –
Figure 6 (right). Vapour entropy diagram (see Figures 5 and 6). Low values of give a
dome of a typical refrigerant vapour dome such that a compression process starting on the
(HFC123) with positive slope
saturated vapour line terminates in the superheated vapour re-
of the saturated vapour line.
gion. With a high value of , however, the vapour dome is
‘undercut’ so that an adiabatic compression process terminates in
the two-phase region. Such a ‘wet’ compression must be avoided
for most types of compressors. The liquid and vapour sides of the
two-phase region are connected and thus high values of also
result in greater flash losses (entropy generation) in the expansion
device. The result of these offsetting effects is an optimum value
for lying between 40 and 100 J/mol-K depending on the
critical temperature of the refrigerant. The optimum value of
results in a vapour dome that gives a small superheat; this is the
behaviour observed with most common refrigerants.
released substances may require many days to years to take effect. In addition to
These effects are widespread and may affect locations far away thermodynamic and
from the source. Hence, these issues are to be tackled on a global thermophysical
basis. properties, possible
environmental
On the other hand, toxicity effects are generally localised and
impacts, safety,
immediate. The margin of safety from the viewpoint of toxicity
toxicity and
depends on the degree of concentration and the duration of
flammability. It is
exposure to cause harmful effects. An ideal refrigerant should be essential that all newly
non-toxic to humans, animals and plant life even at low concen-
considered fluids
trations and with long time exposure. should possess zero
The main concern with the use of hydrocarbon refrigerants is ODP, and low GWP.
their flammability especially in case of leaks. Small- and
medium-sized refrigeration systems use ‘hermetic’ compressors
(compressor and motor placed inside a single sealed shell). Large
systems, on the other hand, use open-type compressors that are
difficult to seal completely. Similarly, a small amount of leakage
also can occur from other components such as valves, measuring
and safety equipment, etc. Refrigerant leaks are therefore diffi-
cult to avoid in large systems. The degree of hazard expected by
the use of a refrigerant depends on factors such as the quantity of
refrigerant used, volume of the space into which the refrigerant
leaks, type of occupancy of the room, risk of naked flame or
electric sparks.
With the increasing erants (supermarkets, concert halls, auditoria, etc.), hydrocarbon
concern for global refrigerants can serve as primary refrigerants in the plant room
warming, it is likely while secondary refrigerants such as propyleneglyocol or
that the refrigeration ethyleneglycol can be used inside the building enclosure. With
industry will have to the increasing concern for global warming, it is likely that the
learn to adopt refrigeration industry will have to learn to adopt flammable
flammable refrigerants even in large applications.
refrigerants even in
Another essential characteristic is the chemical stability within
large applications.
the refrigeration system so that the refrigerant does not decom-
pose when it is repeatedly compressed/expanded and condensed/
evaporated. It should not react with the lubricant or system
construction materials to form harmful compounds. However,
once emitted, a refrigerant should not be so stable that it persists
indefinitely in the atmosphere to reach the upper layers of atmo-
sphere. The ideal refrigerant should be totally stable while in use
6
High oil solubility ensures that but decompose quickly into safe substances when released. These
the compressor lubricating oil contradictory requirements essentially limit the number of fluids
carried over by the refrigerant
that can be used as refrigerants.
returns to the compressor and
does not accumulate in other
Other Properties
components of the refrigerator
such as heat exchangers, pipe-
In addition to the various properties discussed so far, a number of
lines, etc. High vapour dielectric
strength ensures that there is no other practical criteria are also necessary. Oil solubility and high
electric short circuit between the vapour dielectric strength6 are most important for hermetically-
motor windings and the outer sealed compressors. HCs, CFCs and HCFCs are compatible with
shell through the refrigerant
mineral oils, while HFCs are not. Synthetic lubricating oils such
vapour in the case of hermetic
compressors. as polyolester (POE), polyalkyleneglycol (PAG), etc., need to be
used with HFC refrigerants. Since these lubricating oils are also
hygroscopic they cannot be exposed to the atmosphere for more
than a few minutes during maintenance and service activities.
The ideal refrigerant Freezing point of lubricants should be below the lowest expected
should be totally system temperature.
stable while in use
but decompose Economic operation is mainly related to thermodynamic and
quickly into safe thermophysical properties which govern the efficiency and there-
substances when by the energy consumption of the system. Energy saving has
released. significant indirect influence on the environment as it reduces the
Chloroflurocarbons (CFC)
These are fully halogenated fluids that have high ODP and were
found to be the most responsible for the creation of ozone hole.
Use of formerly popular CFCs such as R12 and R11 in new
equipment was banned by the Montreal Protocol. While R12
recovered from old systems may still be available, new lots of
CFCs are no longer being produced.
Hydrochlorofluorocarbons (HCFC)
Hydrofluorocarbons (HFC)
Hydrofluorooelifins (HFO)
Fluoroiodocarbons (FIC)
used as ‘O’ rings, valve seats, seals and gaskets are compatible
with hydrocarbon refrigerants. These include neoprenes, vitons,
nitrile rubbers, PTFE and nylon. Evaporators and condensers
using hydrocarbons tend to be virtually of the same design and
size as those used for conventional fluorocarbon refrigerants that
operate at similar pressures. Heat transfer coefficients tend to be
higher for most hydrocarbons. Most compressor types are also
suitable for use with hydrocarbon refrigerants. Compared to
CFCs or HFCs, a much smaller refrigerant charge is normally
required when hydrocarbons are used.
refrigerants, possible use of air for on-ground applications is Water has many
being considered actively. It should be noted here that the tech- desirable
nology with air as refrigerant will be totally different from that characteristics for
with other working fluids due to the fact that air does not undergo cooling applications
phase change (condensation/evaporation) at the temperature lev- such as; thermal and
els encountered in conventional refrigeration applications. chemical stability,
neither toxic nor
Use of carbon dioxide as refrigerant dates back to the early years
flammable, high COP
of refrigeration. It is environmentally benign. Being the by-
and high heat
product of many energy conversion processes, it is cheap and
transfer coefficients.
easily available. Its use as a refrigerant can reduce its release to
the atmosphere, thereby making a positive contribution to the
environment. Very high operating pressure is a drawback. Be-
cause of its low critical point, most of the thermodynamic cycle
operates in the single phase region. Since CO2 enters the expan-
sion valve as a superheated vapour, it results in a large energy loss
during the throttling process. Carbon dioxide is an excellent 7 The dew point is the tempera-
refrigerant when both heating and cooling are desired. Also, it is ture at which the saturated
not preferable for use in tropical countries such as India due to the vapour starts to condense. The
bubble point is the temperature
high ambient temperatures which result in high condensing
at which the liquid starts to boil.
pressures. In the case of a single compo-
nent fluid, both these tempera-
Blends and Mixtures tures have the same value, i.e.,
at a specified pressure, the fluid
A number of refrigerant mixtures are used for a variety of boils and condenses at the same
applications. Blends or mixtures are used either to obtain differ- temperature. However, in the
ent desired properties such as bubble point temperature, oil case of fluid mixtures, as shown
in Figure 8, the two tempera-
solubility, flammability, as drop-in-substitutes for older refriger-
tures are different and depend
ants that are no longer produced, etc. by combining different on the concentration of each
fluids or to obtain variable temperature refrigeration. The mix- component of the mixture. In the
tures used in refrigeration systems can be divided into four case of an azeotropic mixture,
as seen in Figure 7, the dew
categories, namely, azeotropes, near-azeotropes, zeotropes and
point and the bubble point are
very wide boiling zeotropes. identical just like a single com-
ponent fluid. The line joining the
Figure 7 shows the bubble and dew lines7 of a typical azeotropic dew points at different concen-
mixture. The bubble and dew point temperatures are the same at trations is known as the dew
the azeotropic composition. The mixture essentially behaves as a point line, whereas that joining
the bubble points is called the
pure fluid at this composition. The boiling point temperature of bubble point line.
Box 4.
Air conditioning for comfort and commercial applications such as office buildings, district cooling, malls,
hospitals, information technology and telecom, etc., is a major area which is impacted by the need for change
of refrigerants. Currently, many HFCs, HCFCs and mixtures such as R22, R134a, R404A, R407C and R410A
are in use for this purpose. While these are known to be efficient, they suffer from high GWPs. The most recent
alternatives offer dramatic reductions of GWP between 50 and 99 per cent. A new HFC mixture of particular
interest is R407F (R32/125/134a in the proportion 30/30/40). As a replacement for R404A, this refrigerant
yields nearly 50% GWP reduction, as well as energy savings. It is non-toxic, non-flammable, has properties
similar to R22 and is of interest to supermarket operators. Environmentally-friendly chillers are also being
developed and commercialized based on HFO1234ze, giving reduced energy consumption and also over 99 per
cent reduction in GWP compared to R134a. In most cases, the HFO replacements are compatible with existing
equipment designs and compressors, and therefore can yield quick and cost-effective solutions.
Traditional cascade refrigeration systems used for production of very low temperatures employ separate
compressors and different refrigerants in each of the stages. Mixed refrigerant cascade systems employ a single
compressor operating with a zeotropic mixture of refrigerants to provide cooling with much smaller working
pressures (Discharge:15-20 bar / Suction:3-5 bar) compared to conventional cryogenic cooling systems.
Mixtures with at least four or more components are used in these systems. The refrigerant glide is very large
and is typically over 100 K. In comparison, zeotropic mixtures used in traditional refrigeration systems have
glides less than 6 K, and are made of only two or three components.
9
In a traditional cascade refrig- class of refrigeration systems known as mixed refrigerant cas-
erator, temperatures lower than
cade9 (MRC) refrigerators and liquefiers (see Box 5). Figure 9
–35oC are normally obtained by
using two refrigeration systems shows a schematic of the MRC refrigerator. Mixtures of nitrogen,
operating with different refriger- methane, ethane, propane, and butanes are used in these systems.
ants in each of the cycle, with It is also possible to use HFC refrigerants in mixtures. Tempera-
the evaporator of the first stage
tures as low as 70K can be reached in a single stage with
cooling the condenser of the
second stage. compressor operating pressures similar to those in air-condition-
ing systems. These refrigerators have replaced traditional cas-
cade refrigerators (multistage refrigerators operating in series
with different fluids in different stages) and conventional gas
cycle systems, many in low temperature applications. The main
advantages of MRCs are their higher COP, lower capital cost
.n 5 g
. .
- Wc Qo Evaporator
1 2a 2
. 3 4 .
Q
n Expansion
Compressor Aftercooler Heat exchanger valve
450
2a
400 (a)
20 bar 2 bar
350
)
(K Ambient temperature 2
T 300 1
, 5
Figure 9. Mixed refrigerant e
r
u
t 250
cascade refrigerator: State ra
e
p
m 200
points 1–5 of working fluid e
T
150
shown on the schematic cor-
GRS
respond to those shown on 100 3
4 g
the temperature – entropydia- - 300 - 280 - 260 - 240 - 220 - 200 - 180 - 160 - 140 - 120 - 100
Entropy, s (J/m ol.K)
gram.
Concluding Remarks
The refrigeration industry has seen the rise and fall of a large
number of refrigerants during the last 150 years. CFCs probably
survived the longest till it was proved that they were the major
cause of ozone depletion leading to the ozone hole. HFCs that
replaced CFCs in the last decade have high GWP and need to be
eventually phased out. Environment friendly natural refrigerants
such as ammonia, carbon dioxide, hydrocarbons have specific
practical deficiencies that limit their universal use. Recently
suggested HFOs have low GWP compared to natural refrigerants,
but are flammable.
Address for Correspondence Thus, there are no refrigerants in the horizon that completely
G Venkatarathnam meet the safety, stability, energy efficiency and environmental
S Srinivasa Murthy friendliness. It seems that the refrigeration industry will have
Refrigeration and
very little choice but to use flammable refrigerants (HFOs, low
Airconditioning Laboratory
Department of Mechanical GWP HFCs, HCs, NH3, etc). Since the energy efficiency of HFOs
Engineering is somewhat low, mixtures of medium GWP fluids such as R32
Indian Institute of Technology and low GWP refrigerants such as R1234yf may be the working
Madras
fluids of choice in the immediate future. Meanwhile, the quest for
Chennai 600 036, India.
better molecules continues. Barring new inventions, natural re-
frigerants appear to be the best choice in the long term.
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