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CO2 (R744) REFRIGERATION GUIDELINES

C.J.Hewetson 7 january 05
Revised 23 April 05

1) General
Many people perceive CO2 refrigeration systems as new technology, this perception is incorrect.
CO2 along with SO2 was a widely used refrigerant in the late 19th century until the advent of safer Freon
refrigerants, patented & introduced in the early 20th century. What's new is the fact that few people are
familiar with the benefits, safety aspects, usage & application design requirements of CO2 refrigeration
plant. Additionally, there are few refrigeration products & components commercially available suitable for
system design pressures of 35-50barg, although if CO2 usage increases, no doubt products + sources will
increase.
What is CO2? it is Carbon Dioxide a chemical compound formed by 1 Atom of Carbon & 2 atoms of
Oxygen. It is environmentally friendly with an ODP = 0, GWP =1.
Under normal atmospheric temperature & pressure CO2 exists as colorless, odorless (depending on
concentration), non toxic non flammable gas. Its specific gravity or relative density is 1.524 at 0degC, so
it's heavier than air & will therefore tend to sink to the floor in a confined space or non ventilated area.
If compressed & cooled to a low enough temperature the gas liquefies. Liquid CO2 is produced by
compressing & cooling CO2 gas, liquid CO2 cannot exist as liquid at atmospheric pressure. It must be
pressurized above 60.4lbf/in2 (4.1barg) (-56.6degC) to remain as liquid. At this pressure, which is the
Triple point, CO2 can exist as a solid, liquid or gas. Below this pressure it will flash to a gas and solid.
Above 1056lbf/in2 (72.8barg) 31.1degC which is the Critical point CO2 cannot exist as a liquid. Generally
CO2 is delivered & maintained at or below 0degC 300lbf/in2 (20.68barg)
Solid CO2 or dry ice is produced by expanding liquid CO2 to atmospheric pressure which forms very low
temperature snow. The snow is then compressed to form blocks or pellets, the temperature of dry ice is
-78.5degC at atmospheric pressure. Solid CO2 or dry ice sublimates directly from a solid to a gas. In view
of the temperature of dry ice great care must be exercised in handling it. The need for this caution will
occur if the relief valves relieve liquid CO2 or liquid leaks arise.
CO2 liquid has a high heat of vaporization of 276.8Kj/Kg @ -16.7degC (20.8barg), at this temperature its
density is 1010Kg/m3.
2) Safety issues
The potential safety issues associated with high pressure CO2 refrigeration systems have not been studied
in depth.
Two main issues can however be identified:
High pressure gas/low temperature liquid handling, the potential for tubing, vessels & hose ruptures to
be quite violent.
The potential consequences of an evaporator or condenser or piping rupture & rapid release of the
entire CO2 charge into the plant room or freeze rooms. A rough estimate is that 10 kg CO2 charge
released into a small freeze room or plant room would increase the CO2 concentration to 20%, a level
that will result in rapid unconsciousness followed by death. Note that Tablia Biologica indicates that
9% is the lethal concentration of carbon dioxide for healthy adults. For elderly individuals & those
with impaired health, the lethal concentration is probably around 5%. More work is needed to
determine the likely duration of high CO2 concentrations compared to the range of human tolerance
for these concentrations.
Many people inaccurately believe that as the safety data sheets for CO2 describe the product as non toxic,
non flammable it is safe. This is not correct; a CO2 leak can be fatal. As CO2 levels increase above 2%
in air, you may feel drowsy, at 3% the gas has a narcotic effect, blood pressure rises & hearing may
become impaired. When levels reach 5% difficulties in breathing will be experienced & as CO2 levels rise
above 5% unconsciousness will occur. This is particularly of concern to plant operators & service

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personnel who may be changing oil, overhauling compressors at low level, whereby unconsciousness
arises without any forewarning apart from a feeling of drowsiness.
Additionally CO2 storage systems may be under extremely high pressure due to the steep temperature
pressure curve for CO2, particularly during refrigeration plant shutdown or emergency shutdown & if the
system is not designed correctly with piping & vessels correctly insulated & or standby chilling system to
keep the CO2 below the system MAWP, the relief valves will lift resulting in loss of charge.
Plant designers & plant owners therefore need to ensure that CO2 monitors are installed in the plant room
plus any other cold rooms or confined spaces where CO2 could leak. Additionally regular leak checks
need to be undertaken using electronic CO2 snuffer detectors or Infra Red CO2 detectors. Annual
inspections of all CO2 plant must be undertaken by a competent engineer.
Owners & designers have a duty of care to ensure the plant is correctly & safely designed to meet health &
safety aspects & ensure they are not compromised. In this respect a "Risk Assessment" or "Hazop" study
must be undertaken prior to commissioning any CO2 plant. Service engineers must be fully familiar with
the special safety precautions of charging & evacuating CO2 system, for maintaining the system dry &
checking charge levels without the aid of liquid line sight glasses. Commercially available CO2 should be
98% pure with no moisture content. During plant overhaul the system must be evacuated properly to at
least 5micron or 5mmHg to ensure all moisture is removed. If the system experiences excessive levels of
moisture, whilst tolerable in R717 or R22 pant, will lead to Carbonic Acid production & Carbonic Acid
corrosion on the internal parts of the system.
When designing CO2 plant it is vital that no trapped pockets are produced in the piping or
instrumentation, failing which rupture of components could arise during plant shutdown if the trapped
pocket has no means of relieving the pressure.
3) Plant shut down
Industrial refrigeration CO2 systems will generally operate at sub critical temperatures & pressures or low
pressure. The term "Low pressure" for our purposes is used to describe a sub critical system pressure below
35barg so it is not really low. Generally CO2 is only used in sub critical Cascade 2 stage systems in the low
stage part of the system. The low stage CO2 compressed gas is condensed in the cascade condenser using a
high stage R717 or R404A or R22 direct refrigeration system or using a glycol chiller circulating glycol
through the condenser.
However in hot climates like Saudi Arabia where summer design ambient or plant room temperatures
>50degC are often encountered, extra storage & safety precautions need to be considered for emergency or
planned shutdown of the plant, or a malfunction arises in the high stage system & controls. Loss of
condenser coolant, power failures, compressor failure, controls failure, condenser tube leaks all have the
potential to shut the plant down at any time & for extended periods. With the high stage inoperable,
pressures in the low stage will increase rapidly beyond the relief set point and the CO2 charge will be lost.
To counter this problem, which is not such a problem in European climates with an average ambient
temperature of 15-18degC for most of the year, the low stage system must be fitted with a stand alone
Copeland or Bitzer small hermetic chiller air cooled condensing system & the system must be fully
insulated with a minimum of 50mm Urethane insulation.
If the CO2 low stage system is designed for MAWP of 30barg, DWP 25.4barg, the CO2 must be
maintained at a temperature no higher than -10degC.
For a system designed for 30barg, the only way to guarantee the CO2 system pressure will remain within
the MAWP during system shut down is to include
a) Insulation of the suction, discharge, liquid feed piping plus the cascade condenser and or liquid receiver
if used. The purpose of insulation is to reduce heat gain into the system & to prevent frost build up on
the outer surface. If the storage vessel is insulated with 3" Urethane insulation fully vapor proofed &
Aluminum jacketed, this should maintain the system temperature below the critical temperature or the
MAWP for at least 4 days, which provides a reasonable duration to fix any problem. This is based on a
heat transmission of approximately 100btu/sqft/24hr for a 55degC delta t. If it is anticipated that longer
periods of shutdown will arise, system cooling can be achieved by venting gas from the receiver to

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atmosphere to lower the pressure, alternatively the vessel should not only be insulated but also a
standby chiller should be installed as described in b).
b) Install a stand alone DX R404A or R134A air cooled condensing unit to cool the CO2 in the condenser
or storage receiver via a cooling coil located in the storage vessel or cascade condenser. Based on the
above insulation a small Blitzer or Copeland R404A or R134A condensing unit can be used. For Saudi
Arabia the cooling system should be designed for -15degC ET + 65degC CT. For most CO2 systems a
1-3kw condensing unit should be sufficient to take care of the heat transmission into the system
assuming 3" Urethane insulation.
The cooling coil should be located in the storage receiver, below the liquid level & the system should
include all necessary shut off, solenoid valves, filter driers, sight glass, TEV with automatic CO2
pressure cycling controls in order the unit will stop & start automatically whenever the system pressure
rises above the set point.
During evaporator defrost; the coils will need to be pumped down. It is unlikely that all of the system
charge can be safely held in the condenser, which is another good reason for providing an HP receiver.
If no receiver is included in the system, then it may not be possible to inspect the cascade condenser or
carry out tube leak repairs/replacement without removing the CO2 to a separate refrigerated road tanker.
CO2 refrigeration plant designed for Saudi requires stringent design & safety features to maintain the
system temperature & pressure below the CO2 critical temperature of 31.1degC or 72barg. In any event it
would be impractical to design the system for 120barg which is used for super critical automotive A/C.
4) Storage HP receivers
Storage tanks or vessels for CO2 refrigeration differ little from commercial CO2 tanks for the Brewing &
drinks industry, the same design & safety elements apply. The liquid storage vessel consist of a welded
steel pressure vessel designed, constructed, and tested in accordance with the requirements of ASME V111
Div1 Boiler and Pressure Vessel Code applicable to storage unit construction, for Unfired Pressure Vessels
or for EC sourced vessels PED. The storage vessel is constructed using high strength, fine grain carbon
steel ASTM SA-612 or 516 grade 70N based on the design operating temperature & pressure. The storage
vessel MAWP will depend upon the application, but generally would have to be 35barg at the minimum
designed metal temperature (MDMT).
Liquid CO2 storage vessels should be designed, constructed and tested for specific operating pressures and
fill rates with full system charge storage @ 80% receiver volume & maximum expected standby
temperature. CO2 vessels must never be allowed to become completely full at the pressure relief device
setting. The MAWP of a CO2 storage vessel should be 10-20% above the design working pressure DWP.
The relief valves must be set at the MAWP, the relief valves must be located such that only gas is
discharged straight to atmosphere. No discharge relief piping should be included, to ensure that the relief
valve discharge does not become blocked due to freezing or dry ice blocking the relief line.
Instrumentation supplied with all CO2 storage vessels/systems should include the following:
1. 0 to 600 psi (4137 kPa) pressure gauge with a 6" (15.24 cm) dial face. This gauge gives the operating
pressure of the storage unit at all times.
2. A gauge is used to indicate capacity in the storage unit. The differential liquid level gauge has a 6"
(15.24 cm) diameter dial face, calibrated to read in kilograms and pounds of liquid carbon dioxide.
3. High and low audible pressure alarm. This alarm monitors the pressure of the storage unit. If the
pressure fluctuates outside of normal operating conditions, an alarm will sound.
4) CO2 temperature & pressure sensors to automatically cycle the refrigeration standby unit.
5) CO2 plant room & freeze room monitoring system

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CO2 is compatible with most metallic piping materials. There are piping hazards associated with liquid
carbon dioxide storage units such as elevated pressure. Corrosion is typically a problem only on the
exterior of piping that is subjected to moisture condensation from temperature cycling. However internal
corrosion may arise depending on moisture content of the CO2 due to Carbonic Acid attack. All vessels
should include at least a 2mm corrosion allowance or in accordance to the code.
All piping and fittings furnished as a part of a CO2 storage unit should be seamless schedule 80 carbon
steel. Fittings can be weld or screw type 2,000 Lbs (907 Kg) forged steel. All nozzles and valves that
penetrate the outer jacket should be stainless steel.
Depending on CO2 storage capacity/vessel size & code requirements, a man way should be included as
standard equipment. The man way serves two purposes:
1. Internal inspection.
2. Cleaning inside of the storage vessel.
There has been discussion within certain regulatory agencies in the United States that may require periodic
hydrostatic testing and internal inspections of all storage vessels. If these regulations become mandatory,
then the man way will play an important role in compliance with these regulations.
A refrigeration coil should be installed as standard equipment on the Urethane insulated storage vessels as
previously indicated. However as an alternative CO2 can be vented in gas form the storage vessel, a self
refrigeration effect occurs as the pressure in the storage vessel is reduced. This self refrigeration effect is
more pronounced in vapor venting. For every pound of vapour vented, approximately 120 BTU/lb is
removed.
5) Compressors/components
Most reciprocating & screw compressors will not be suitable for CO2 operation due to design pressure
limitations of 25barg. Generally cast steel housings are required to withstand the pressure. Sabroe provide
reciprocating compressors HPO/HPC range rated at 40barg & using Nodular Iron casing can use screw
compressors rated at 35barg. Frick can provide optional cast steel housings as standard. Bitzer also have a
good range of CO2 compressors.
In terms of screw compressors the factory should check any selection in terms of radial/axial bearings L10
life, in view of the potentially high compression ratio of CO2 compressors operating at -45 & -5degC.
They should also provide a recommendation for the correct lubricating oil.
Danfoss have a total range of relief, stop, check, regulating, solenoid valves, filter driers rated at 50barg,
there are also many other manufacturers of cast steel valves suitable for 50barg. Solenoid coils may need to
be dc voltage 20watt to cope with the additional forces arising from high differential pressures.
In terms of service shut off valves high pressure cast steel long neck ball valves should be used to allow
for adequate insulation. These are readily available from many manufacturers. CO2 filter driers, valves,
gauges, HP/LP controls are also readily available from conventional CO2 storage tank suppliers or CO2
suppliers.
All suppliers must be advised the compressors & components are for CO2 usage in combination with POG
synthetic oil to ensure the compatibility with materials of construction.
CO2 piping can be carbon steel schedule 80 ASTMA SA 333 grade 6 which is suitable for operation from
0degC to -46degC. Forged steel flanges should be SA 350LF2, Wrought fittings should be SA 420WPL6.
316 stainless steel tube & fittings should also be considered for CO2 systems as this reduces the risk of
corrosion externally due to condensation or internally due to Carbonic Acid attack.
Charging hoses should be rated @ 120barG minimum & gauges + differential gauges used to check charge
levels must be 6" dial type rated at 50barg minimum.
The pressure relief valves on the high stage R717 system must be rated in accordance to API 526 & RP520
with the relief rate based on burst tube conditions which may arise if a tube in the cascade condenser leaks
or bursts. The relief rate calculation should be based on CO2 not equivalent air flow rate.
Evaporators can be standard Cu/Al air coolers with suitably modified circuitry for CO2 operation if

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considered necessary by the manufacturer. Most manufacturers provide an option of 316 stainless steel
tube coolers if the system designer perceives corrosion may be an issue during operation or service. In all
cases the MAWP should be checked with the manufacturer as in general this information is not provided in
their catalogues or computer printouts. If shut off valves are provided at the cooler inlet & outlet a suitably
CO2 rated relief valve must be installed.
Defrost can be similar to normal electric or hot gas system designs, however it is vital that the compressor
can operate on a continuous pump down cycle to ensure evaporators are properly evacuated prior to
energizing the defrost system so the evaporator pressure is kept below the relief valve set point during
defrost.
Generally electric defrost is preferable to Hot gas systems. With hot gas it may not be possible to provide
enough gas with a high enough enthalpy to quickly defrost due to the cooler pressure limitations or relief
valve settings e.g. if the system design condensing temperature is -5degC the discharge temperature will be
approximately 67degC @ 30.8bara & the enthalpy difference around 244kJ/kg. On a normal R717 hot gas
system the discharge gas is at a temperature of around 132degC @16.4bara with an enthalpy difference of
around 1,056kJ/kg.
The system saturated operating pressures must not drop below 5.5barg e.g. evaporating temperatures below
55degC are not possible as the CO2 will solidify & the plant will stop.
6)

Supercritical/subcritical/Transcritical CO2 systems

A supercritical fluid is defined as a substance that is at conditions of temperature and pressure that are
above its vapor-liquid critical point. At supercritical conditions, a fluid does not meet the definition of a
liquid because it can't be made to boil by decreasing the presssure at constant temperature. Also it is not a
vapor because cooling at constant pressure won't cause it to condense. Water is a supercritical fluid above
374degC 22 MPa, CO2 is a supercritical fluid above 31degC & 72.9atm 5.5bar
Supercritical fluids in general possess unique transport properties compared to liquids or gases.
Supercritical fluids can have liquid-like densities, gas-like diffusivities, and compressibilities that deviate
greatly from ideal gas behavior.

Fig.1 Phase diagram for R 744.

The three well-known phases: solid, liquid and vapor are shown in Fig. 1. The boundaries between them
represent the well known phase change processes like evaporation and condensation for the boundary between
liquid and vapor phases (vapor pressure curve). Two important state points are marked on the figure: the triple
point and the critical point. The triple point represents the condition where all three phases can co-exist in
equilibrium. At temperatures below the triple point temperature, liquid cannot exist. In other words, the triple
point temperature sets the lower temperature limit for any heat transfer process based on evaporation or
condensation. At the other end of the vapor pressure curve the critical point marks the upper limit for the heat
transfer processes. At temperatures above the critical temperature, all heat transfer processes will be singlephase processes. The term critical is not used in the sense of "dangerous" or "serious", rather it is used to
represent the condition where distinguishing between liquid and vapor becomes difficult.
The termination of the vapor pressure curve at the critical point means that at higher temperatures and
pressures no clear distinction can be drawn between what is called liquid and what is called vapor. Thus, there

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is a region extending indefinitely upward from, and indefinitely to the right of, the critical point that is called
the fluid region. This region is bounded by dashed lines that do not represent phase transitions, but instead
conform to arbitrary definitions of what is considered a liquid and what is considered vapor.
Table 1. Critical properties of selected refrigerants.

Refrigerant

Critical
pressure
Bar a
R22
49.9
R134A
40.6
R404A
37.3
R410A
49.0
R600a
36.4
R717
113.3
R744 (CO2) 73.8

Critical
temperature
degC
96.1
101.1
72.0
71.4
134.7
132.3
31.0

All substances have a triple point and a critical point, but for most of the substances used as refrigerants, the
triple point and critical point are found for conditions that lie outside the region where they are normally used.
Table 1 compares the critical pressure and temperature of a number of common refrigerants.
The critical temperature means that heat rejection processes by condensation can be established at
temperatures up to the critical temperature, which is a temperature higher than necessary for rejecting heat to
the ambient for almost all refrigeration applications. Most commonly used refrigerants have a critical
temperature above 95 C, but some of the refrigerants such as those indicated R 404A, R 410A & R 744,have
critical temperatures below that which means normal heat rejection processes are not possible.
For R 744, the critical temperature is only 31.0C. This means that R 744 heat rejection process by
condensation can only be established at temperatures up to 31C, which is a temperature much lower than
necessary for rejecting heat to the ambient applicable to most countries except some in Northern Europe.
Considering the temperature difference needed in a heat exchanger, a practical upper limit for a heat rejection
process based on condensation of R 744 is reached at ambient temperatures around 20C.
For many refrigeration applications, the ambient temperature will exceed this value, certainly here in Saudi
Arabia. However, this doesnt mean that carbon dioxide cannot be used as a refrigerant in applications
rejecting heat to the ambient at temperatures above 20C. Carbon dioxide can indeed be used as a refrigerant
for these applications, but the heat rejection process from these applications cannot be based on condensation.
There are three refrigeration cycle processes:

Sub critical, where the pressure in all parts of the refrigeration system is kept below the critical
pressure.
Super critical, where the pressure during the heat rejection (condensation) process is above the critical
pressure.
Transcritical, where some parts of the refrigeration cycle process take place at pressures above the
critical point & others parts below the critical pressure, the refrigeration cycle process is referred to as
a transcritical cycle process. In the transcritical cycle process, the heat rejection takes place at
pressures and temperatures above the critical point.

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The terminology used for the processes and the components are almost the same for the three cycle
processes except for the heat rejection parts. In the transcritical cycle process, the heat rejection is called
gas cooling and subsequently the heat exchanger used is called a gas cooler.
7) R744 cycle benefits
In general terms CO2 will not be the 'Holy Grail' environmental refrigerant replacement. There are inherent
dangers in its application & usage, few components are readily available, users & service engineers require
specialist training in handling & servicing techniques. Its COP is no better than most other currently available
environmentally friendly refrigerants such as R134a or R404A. Its COP is only possibly superior at low
temperature e.g. -40degC. The best way to indicate the benefits of R744 applied to low temperature booster
applications is to compare an R744 HPO 28 high pressure 40bar low stage compressor to the nearest
equivalent SAB R717 25bar screw compressor, operating at the similar conditions as per Table 2. It can
readily be seen that the major advantage of R744 at these conditions only, is not just its zero ODP & GWP of
1, but higher COP/EER or Kw/Kw which provides lower shaft power, smaller Kw rated drive motors-starters,
cables + much lower compressor displacement e.g. for an equivalent duty using R717 you would require a
compressor with 8 x larger displacement due to the difference in the suction gas specific volume. In terms of
safety aspects between the two systems it is again fair to presume that R744 systems are overall probably safer
than R717 systems, on the basis both require equal special safety precautions. R717 is flammable as well as
toxic with a classification of B2, as against A1 for R744, which requires even greater safety precautions. In
some countries system design may have to conform to Zone2 or Division 2 hazardous area requirements. In
other countries R717 systems can be dealt with by "special protection" in a manned plant room e.g. IP55
TEFC motors, R717 leak detectors & monitoring system linked to an extract fan with exhaust stack. So for
both R744 as well as R717, leak detectors & monitors plus ventilation extract fans & exhaust stacks would be
a requirement.
Description
R744 value
R717 value
Compressor
HPO28
SAB202L
Compressor capacity
289.4Kw
277.6Kw
Compressor shaft power
77.2Kw
98.7Kw
Kw/Kw
0.267
0.356
Kw/TR
0.933
1.24
Suction pressure
8.16 BarA
0.53 BarA
Suction temperature
-45degC
-45degC
Discharge pressure
26.83 BarA
2.97BarA
Discharge temperature (actual)
46.6degC
77.15degC
Condensing temperature
-10degC
-10degC
Suction mass flow rate
1.121Kg/s
0.2232Kg/s
Suction specific volume
0.0469M3/kG 2.0591m3/Kg
Enthalpy difference
267.64kJ/Kg 1,244.17kJ/Kg
Compressor swept volume
226.3m3/h
1919m3/h
Liquid density
983.2Kg/m3
652 Kg/m3
Pressure ratio
3.29
5.6
Gas safety group
A1
B2
Table 2. Comparison of performance for R744 & R717 based on HPO 28 + SAB202L compressor &
same operating conditions.