Introduction to Alternative Refrigerants other than HFC

Alternative Refrigerants
other than HFC
Introduction to Alternative Refrigerants other than HFC

1. Brief History

R744, R717 and R290 were among the earliest refrigerants used for mechanical
cooling systems. Their use declined when CFCs and HCFCs were developed and
R744 and R290 were rarely used. R717 continued to be used in industrial systems.
When the ozone depleting refrigerants1 were phased out R290 and other
hydrocarbons started to be used again. At the same time HFC refrigerants were
introduced and widely used, but their high global warming potential coupled
with high leak rates in some applications has caused some of the industry to
use lower GWP alternatives. These include R744 which has been used in retail
systems since the year 2000, and lower GWP HFCs.

2. Basic Properties

The basic properties of these refrigerants are shown in Fig 1.

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Introduction to Alternative Refrigerants other than HFC

Some of these refrigerants are already widely used, others are starting to be trialled
and deployed. Their application is often limited by flammability and toxicity - Fig 2.
below summarise the applications they are most suitable for.

Flammable refrigerants are categorised as having either lower of higher flammability,

dependent on the concentration required for ignition to be possible, the heat of
combustion and flame propagation. Lower flammability does not mean non-
flammable.

Fig 2.

Fig 2. indicates the type of system the refrigerant is most appropriate for – it does
not show where these refrigerants are actually being used. Fig 3. below gives more
information on current applications.

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Introduction to Alternative Refrigerants other than HFC

Green – these systems are suitable for the refrigerant type indicated,
and the charge size is usually within the limits specified in EN378.
Some design changes are required, for example to electrical devices
and / or ventilation.

Amber – these systems can and are used with the refrigerant type
indicated, but there are restrictions because of the maximum charge
or practical limit specified in EN378 (The practical limit for refrigerant
represents the concentration used for simplified calculation to
determine the maximum acceptable amount of refrigerant in an
occupied space. It is based on either toxicity or flammability. For full
information see EN378 Part 1).

Some design changes are required to electrical devices and / or

ventilation. In some cases, the volumetric capacity of the refrigerant
means it is not ideal for the application.

Red – these systems should not be used with the refrigerant type
indicated, usually because the charge size exceeds the maximum
specified in EN378-1.

Fig 3.

3.

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Introduction to Alternative Refrigerants other than HFC

4. R744 (carbon dioxide, CO2) GWP = 1

R744 has high operating pressures, a low critical temperature (31 OC) and a high
triple point. Its volumetric cooling capacity is between 5 and 8 times that of HFCs,
reducing the required compressor displacement and pipe size.

Its properties have an effect on how the system is designed and operates, especially
in high ambient temperatures. It has a high discharge temperature, necessitating two
stage compression for low temperature systems.

R744 is used in the following system types:

 Pumped secondary – where R744 is the secondary fluid cooled by a primary

system. R744 is a volatile secondary which, coupled with the high capacity
and density, reduces the required pump power compared to other secondary
fluids such as glycol.

 Cascade – where the heat rejected by the condensing R744 is absorbed by

the evaporating refrigerant in a separate high stage system. In these systems
the R744 operates below the critical point and the high side pressure is
generally below 40 barg. The high stage system can be R744, or it can be
HFC, HC, HFO or R717.

 Transcritical systems – where the R744 heat is rejected to ambient air and at
ambient temperatures above approximately 21 OC the R744 will be above the
critical point (31OC) – i.e. it will be transcritical. The R744 does not condense
– it remains a super critical fluid until its pressure is reduced to below the
critical pressure (72.8 barg). The high side pressure is typically 90 barg when
transcritical.

R744 has been used in many 1000 retail systems and in industrial systems in
Europe. It is also used in heat pumps and in integral systems.

The application of R744 has required additional skills for design engineers and
service technicians, and availability of new components.

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Introduction to Alternative Refrigerants other than HFC

5. R717 (Ammonia, NH3) GWP = 0

R717 has a relatively high saturation temperature at atmospheric pressure, is highly

toxic, has lower flammability and has a pungent odour. It can be smelt at very low
concentrations of 5 parts per million, so it is evident at levels much lower than those
which are hazardous. It is the only commonly used refrigerant which is lighter than
air which means that dispersion of any leaked refrigerant takes place quickly.

The relatively high saturation temperature means that many low temperature
applications (e.g. frozen food cold rooms and blast freezers) run at sub atmospheric
pressures on the low side.

R717 also operates with very high discharge temperatures. Single stage
compression can therefore normally be used above -10 OC evaporating temperature.
Below this, two stage compression with interstage cooling is required.

The high toxicity limits the application of R717 to very low charge systems or
industrial systems (i.e. systems in areas which are not accessible by the general
public). This typically includes distribution cold stores and food processing plants,
usually using secondary systems where R717 is the primary refrigerant.

Ammonia corrodes copper so steel pipe work and open drive compressors are used.
It is also immiscible with conventional mineral oils, making oil rectification an
additional requirement of the refrigeration systems. The use of steel pipe, open drive
compressors and oil rectification impact on the capital cost of an ammonia
installation.

6. R32 (HFC) GWP 675

R32 is a low flammable HFC. Its performance and operating pressures are very
similar to R410A and it is starting to be used in similar applications – heat pumps,
split air conditioning systems and chillers. For further information on suitability of
application of this refrigerant you should always contact your equipment supplier.

Its lower flammability limits the refrigerant charge size, but not to the same extent as
the more flammable hydrocarbons. Electrical devices on the system will be the non-
sparking type if a leak can result in a flammable concentration around the electrical
device.

The operating pressures are higher than for most HFCs but are similar to R410A.
Typically the high side maximum pressure is 35 barg.

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Introduction to Alternative Refrigerants other than HFC

7. R1234ze and other HFO refrigerants

The main HFO (HydroFluoroOlefin) refrigerants are R1234ze and R1234yf. These
are both pure substances in the same family, consisting of hydrogen, fluorine, and
unsaturated carbon. These are both have lower flammability and have very low
GWP.

An HFO – HydroFluoroOlefin is a halocarbon containing hydrogen, fluorine and

unsaturated carbon.

Their lower flammability limits the refrigerant charge size, but not to the same extent
as the higher flammability hydrocarbons. Electrical devices on the system will be the
non-sparking type if a leak can result in a flammable concentration around the
electrical device.

The saturation temperature of R1234ze at atmospheric pressure is high compared to

other refrigerants so it will operate on a vacuum on the low pressure side of the
system for low temperature applications. It is therefore most suitable for medium and
high temperature applications such as water chillers. Its cooling capacity is also low
compared to other HFCs which means that different compressors are required, with
a larger displacement relative to the motor.

R1234ze is available and used in chillers and integral units.

R1234yf is in widespread use in car air conditioning. It has now started to be used in
commercial chiller applications. It is similar to 1234ze in that it will operate on a
vacuum on the low pressure side of the system for low temperature applications
making it more suitable for medium and high temperature applications such as water
chillers.

However, it has a capacity very similar to R134a which means that the same
compressors can be used.

Several blends using HFOs are in commercial use. They have lower GWPs than
pure HFCs such as R404A and R134a, but some are flammable.

8. R290, R1270 and R600a (HCs) GWP = 3

R290 (propane), R1270 (propene, propylene) and R600a (isobutane) are all
hydrocarbons. They are highly flammable, so refrigerant charge size is limited on
many applications. This limits the application of HCs mainly to integral systems,
chillers, and some split air conditioning systems. Electrical devices on the system will
be the non-sparking type if a leak can result in a flammable concentration around the
electrical device.

R290 and R1270 have similar performance and operating pressures to R404A and
they are used in high, medium and low temperature commercial applications. R600a
has a much higher saturation temperature than other refrigerants and operates at a
vacuum on the low side in most applications. Its use is limited to domestic and very

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Introduction to Alternative Refrigerants other than HFC

small commercial refrigeration systems with minimal leakage so that ingress of air
and moisture due to leakage rarely occurs.

9. Hazards

All alternative refrigerants covered in this guide have additional hazards compared to
the traditional HFC refrigerants. These include:

 Flammability
 Toxicity
 High pressures

Fig 4. below summarises the hazards of the alternative refrigerants. The traffic light

system indicates the severity of the hazard compared to R404A.

Fig 4. For all refrigerants
– risk is reduced by minimising leak potential. For all refrigerants – risk is
reduced by minimising leak potential.
Introduction to Alternative Refrigerants other than HFC

10. Safety Classification

The classification comprises two parts: A or B followed by 1, 2L, 2 or 3.

 A or B represents the degree of toxicity

o A is lower toxicity (most refrigerants are class A)

o B is higher toxicity (R717 is class B).

 1, 2L, 2 or 3 represents the degree of flammability

o 1, non flammable
o 2L, lower flammability
o 2, flammability
o 3, higher flammability.

Fig 5. below lists the safety classification of the common alternative refrigerants.
Introduction to Alternative Refrigerants other than HFC

11. Performance and operating conditions

Fig 6. below provides an indication of performance of the alternative refrigerants.

R404A is included for comparison purposes. This information has been derived
from Cool Pack software except where specified.

The figures below provide an indication of comparative performance as it is based on

a theoretical cycle. Actual comparisons depend on compressor technology,
application, ambient and system type. Manufacturer’s data / software will provide a
more accurate comparison for a specific application.

This is especially so for R744 where expected COP, for example, would be higher
than indicated below for the type of system and operating conditions where R744 is
typically deployed.
Fig 6.

The comparison has been estimated at the following conditions:

Cooling capacity, 10kW

Evaporating temperature, -10OC
Condensing temperature, 35OC (R744 is transcritical and has a gas cooler exit
temperature of 35OC)
Useful superheat, 5K
Subcooling, 2K
Pressure losses are equivalent to 0.5K
Isentropic efficiency, 0.7
Introduction to Alternative Refrigerants other than HFC

11. Environmental impact

Global Warming Potential (GWP)

Fig 7A/B. provides the direct global warming potential (GWP) of the alternative
refrigerants. This should not be considered in isolation when selecting a refrigerant
for a particular application. The impact of the refrigerant’s GWP is much less if the
refrigerant does not leak during normal operation and the system is serviced without
refrigerant loss. However, the revision of the F Gas regulation will necessitate the
application of low GWP refrigerants.

Fig 7A.

Fig 7B.
Introduction to Alternative Refrigerants other than HFC

12. Total Equivalent Warming Impact

The total impact of a system and refrigerant on climate change is estimated using
TEWI – the Total Equivalent Warming Impact9. It is a method of assessing the
impact on climate change over the lifetime of a system by combining:

direct contribution of refrigerant emissions into the atmosphere

+
indirect contribution of the CO2 resulting from energy to operate the system

It is a very useful method of comparing different system and refrigerant options at the
design stage or when considering a retrofit, for example from R404A.

There are many ways TEWI can be minimised, including:

 Minimising refrigerant leakage (which reduces both the direct and indirect
impact because leaking systems use more energy)
 Use of low GWP refrigerants
 Minimising cooling load
 Maximising energy efficiency through appropriate design and installation
 Maintaining the system correctly
 Minimising refrigerant loss during service
 Recovery and recycling of used refrigerant (and used insulation where this
has a blowing agent which has a GWP)

TEWI is calculated as follows:

TEWI = impact of leakage losses + impact of recovery losses + impact of energy

consumption

Impact of leakage losses = GWP x L x n

Impact of recovery losses = GWP x m x (1-αrecovery)

Impact of energy consumption = n x E annual x β

Where:
L = leakage in kg/year
n = system operating time in years
m = refrigerant charge in kg
α recovery = recovery / recycling factor, between 0 and 1
E annual = energy consumption in kWh per year
β = CO2 emission in kg / kWh, note – this varies significantly from country to country.

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Introduction to Alternative Refrigerants other than HFC

13. Leakage issues

.
Whatever refrigerant is used leak potential should be minimised. Low GWP
alternative refrigerants usually have hazards associated with high pressure,
flammability, or toxicity, so leakage is a safety concern. In addition – any leaking
system consumes more power and so has a greater indirect impact on climate
change.

The potential for leakage is a combination of factors such as operating pressure,

molecule size and system size / type. This is summarised in Fig 8. below, with

hazards associated with leakage and ease of leak detection.

Fig 8.

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Introduction to Alternative Refrigerants other than HFC

14. Flammability

The flammability classification is explained in Fig 9. below.

Three conditions are required for combustion – fuel, oxygen (air),

and a source of ignition. Fig 10.

For all flammable refrigerant’s combustion will occur if the

refrigerant concentration in air is between the lower
and upper flammability levels and if there is a source
of ignition.

The flammable range for HCs, A2L refrigerants and

R717 is shown in Fig 11. below (the lower
flammability level is also listed in Fig 5.)
Fig 10.

Fig 9.

Fig 11.

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Introduction to Alternative Refrigerants other than HFC

An open flame will ignite all flammable refrigerants, e.g. a brazing flame, match,
cigarette lighter.

Sparking electrical devices will ignite A3 (HC) refrigerants and possibly 2L

refrigerants.

Sparking electrical devices can include:

 On / off switches, e.g. on electrical sockets, vacuum pumps, recovery

machines
 Contactors
 Light switches
 Standard thermostats
 Standard compressor relays and overload protectors (klixons)
 Standard pressure switches (high pressure, low pressure, oil differential
pressure)
 Standard light starters (ballasts)
 Standard timers (e.g. for defrost) and controllers
 Electronic leak testers

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