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A LL FA C T S
ANT
R E F R IG E R
CO2 AS A

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N EW- O LD R EF R I G ERA N T

Carbon Dioxide for Industrial Refrigeration

By Donald L. Fenton, Ph.d., P.e., Life Member Ashrae | ASHRAE JOURNAL, ashrae.org
ASHRAE CO2’s Physical Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
CO2 Vapor Compression Cycles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
CO2 as a Secondary Coolant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

HERMETIC-Pumpen HERMETIC – Your Partner in CO2 Business for More Than 50 Years. . . . . . . . 20
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Carbon dioxide (CO2) is an old refrigerant, first patented In response to these findings, many countries agreed to halt the pro-
duction of these CFC and HCFC refrigerants within an appropriate
in the United Kingdom in 1850 by Alexander Twinning,
time frame, allowing the ozone layer to replenish. This agreement is
where it was subsequently used in air-conditioning and called the Montreal Protocol where its second and fourth amendments
marine applications. With the development of the CFC, concern CFCs and HCFCs.2,3 At this same time, Lorentzen4,5 proposed
CO2 as an alternative refrigerant for the CFC and HCFC refrigerants.
HCFC, and HFC synthetic refrigerants beginning around
After CO2’s reintroduction, applications first appeared with mobile
1930, CO2 decreased in popularity, all but disappearing air conditioning and heat pump water heaters. Other applications
by 1960. Over the next two decades or so, it was soon followed, which include CO2 as a heat transfer fluid, low-
temperature refrigerant in a cascade refrigeration system, or as
experimentally determined that CFC and HCFC refrig-
the sole refrigerant. In North America, more than 150 supermarket
erants were depleting the earth’s upper atmospheric transcritical and other CO2 systems are in operation,6 and over
ozone layer at a rate that would likely cause its 70 NH3-CO2 industrial subcritical cascade systems operating with
many being planned.7
disappearance.1

3
Transcritical refrigeration cycles involve CO2 gas cooling (rather Scientific study of the atmosphere has revealed that the CO2 in the
than condensation for heat rejection) at conditions above the earth’s atmosphere is a significant contributor to global warming.
refrigerant’s critical point where the refrigerant is called a “super- The important sources of atmospheric CO2 are emissions from
critical fluid” and behaves as a dense gas.8 In contrast, subcritical fossil fuel electrical power generating plants and from combustion
refrigeration systems operate at conditions below the critical point engines powering vehicles of all types. Currently, regulations do not
where phase change, condensation, occurs. The focus of this article limit CO2 quantities that may be vented from a refrigeration system.
is industrial refrigeration where CO2 is used as a refrigerant.
The ozone depletion potential for all the natural refrigerants is
CO2 is a naturally occurring substance because it is present in zero. The global warming potential for these refrigerants is either
the earth’s atmosphere at a concentration of about 404 ppm (v/v). zero, or very small. The global warming potential of CO2 is 1.0
The other substances classified as natural refrigerants are ammonia, (set to this value by definition), where in contrast the CFC and
water, air, and hydrocarbons, all of which are naturally occurring. HCFC refrigerants have values generally exceeding 1,000.

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CO2’s Physical Characteristics
The physical characteristics of CO2 are unique. The thermodynamic Table 1: CO2 and other refrigerant physical properties.9
vapor compression refrigeration cycle, component design, system R-22 R-507A R-404A NH 3 CO 2
design, and operation are constrained by the characteristics of CO2,
Natural No No No Yes Yes
which are shown in Table 1. Note that the freezing point (triple Substance
point) of CO2 is – 56.6 °C (– 69.8 °F), and NH3’s freezing point is Chemical CHClF2 R-125/143a R-125/142a/134a NH3 CO2
– 77.7 °C (– 107.8 °F), both in the same neighborhood. Formula (50.0/50.0) (44.0/52.0/4.0)
Molecular Mass 86.5 98.9 97.6 17.0 44.0
However, the critical temperature of CO2 is 31.0 °C (87.8 °F) and ODP 0.04 0 0 0 0
132.3 °C (270.1 °F) for NH3, much less than NH3’s. While the GWP 1,790 4,000 3,700 <1 1
freezing point (triple point) for CO2 is not much different than NH3’s, Critical Pressure 723.7 537.4 540.8 1,643.7 1,070.0
(psia)
the CO2 critical temperature is significantly less than that of NH3.
Critical Temperature 205.1 159.1 161.7 270.1 87.8
(°F)
R-22, an HCFC whose production is now curtailed, was once a
Boiling Point (°F)a – 41.5 – 52.1 – 51.2 – 28.0 – 109.1b
popular refrigerant for industrial systems. Refrigerants R-507A and
Freezing Point (°F) – 251.4 – – – 107.8 – 69.8
R-404A are an azeotrope and blend, respectively, and both are
Flammable No No No Yes No
HFCs. Their high GWP makes their future as refrigerants uncertain.
Toxic No No No Yes No
NH3, despite its good thermodynamic characteristics, has dis-
Ashrae Safety Group A1 A1 A1 B2L A1
advantages including toxicity and moderate flammability. These
reasons now make CO2 a refrigerant worthy of consideration a
At 14.696 psia; b Sublimes
for many applications in industrial refrigeration systems.

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Figure 1 is a plot of saturation pressure versus saturation temperature
for several refrigerants including CO2 and NH3, which shows: 1,450
■ The absolute CO triple-point pressure 5.18 bar (75.1 psi) is
2 725
above atmospheric pressure.
■ The CO critical-point temperature is less than typical design
2
145

condensing temperature.

Saturated Pressure (psia)

73

Note that CO2 is a low-temperature refrigerant (above atmos­-

pheric pressure at low temperatures) where in contrast, NH3 is an
intermediate-temperature refrigerant. The CO2 phase diagram is p. sat R-507A
14.5
shown in Figure 2 where only essential features are shown. Here the p. sat R-22
latent heat of CO2 is indicated by the horizontal distance between 7.3
p. sat R-404A
the saturated liquid and vapor lines. Comparison to R-22 reveals p. sat NH3
that the latent heat of CO2 is considerably higher than, but not as p. sat CO2
high as, NH3’s latent heat. Also, the CO2 pressure-enthalpy diagram 1.5
shows that CO2 exists with high pressures and low temperatures – – 148 – 112 – 76 – 40 –4 32 68 104 140

the top of the dome (critical point) is only 31.0 °C (87.8 °F). Saturated Temperature (°F)

Figure 1: Saturated pressures and temperatures for several refrigerants.

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Figures 3 and 4 show the saturated liquid and saturated vapor lines
Critical Point
for CO2 and NH3 on p-h (pressure-enthalpy) axes, respectively. 87.8°F
These two charts and the characteristics mentioned above result in
1,069 psia
important and practical consequences when applying CO2 to
industrial refrigeration.

°F
Liquid and
Solid

9.8
Liquid Vapor

–6
Because of CO2’s high pressures, atmospheric air and water are not

Pressure, p
75.1 psia – 69.8°F Vapor
likely to enter the system. And, because CO2’s suction vapor density
is high, compressors are small and evaporators operate with good
performance. Further, observe (Figure 1) that the slope of the Solid Solid and Vapor
pressure-temperature curve for CO2 shows a much greater pressure
change for the same temperature change. In other words, pressure
drops in CO2 result in much smaller temperature drops. For example, 14.5 psia – 109.1°F
saturated CO2 vapor at – 42.8 °C (– 45 °F) with a 0.07 bar (1.0 psi)
pressure drop has a corresponding 0.22 °C (0.4 °F) temperature Enthalpy, h
drop.
Figure 2: Pressure-enthalpy diagram for CO2.9

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In contrast, saturated NH3 vapor at – 42.8 °C (– 45 °F) with 0.07 bar
(1.0 psi) pressure drop has a corresponding 2.0 °C (3.6 °F) temperature
drop that is larger by a factor of about 9 or 10. These consequences
add together, giving CO2 excellent characteristics for subcritical
vapor compression refrigeration cycles.

A concern with CO2 is the possible formation of solid CO2 (dry ice)
in the outlet piping from a pressure safety relief valve blocking
the vapor flow. Observe from Figure 2 that CO2 back pressures
less than the triple-point absolute 5.2 bar (75.1 psi) will result
in the formation of dry ice.

For relief valves connected to a compressor’s discharge or

protecting a liquid separator, the risk of solidification is minimized
when the CO2 discharge is piped to an outlet header. Relief valves
protecting components or vessels containing saturated liquid CO2
should be located outdoors and have no outlet piping to avoid
solidification.

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 HERMETIC solution for CO2

CAM series

CAMh and CAMhk series with

PN52 design for handling CO2

CNF series

Figure 3: Pressure-enthalpy diagram for CO2.10

9
 HERMETIC solution for NH3

CAM series

CNF series

Figure 4: Pressure-enthalpy diagram for NH3.10

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CO2 Vapor Compression Cycles
CO2 Transcritical Cycle
The basic vapor compression refrigeration cycle consists of four Gas Cooler
components where the refrigerant is conveyed to and from the Compressor
Fadeout
components by the interconnecting piping. Figure 5 is a schematic Vessel 3 2
showing these components and how they are connected to each
other. Figure 6 is a p-h diagram of CO2 where the cycle state points
4 1
are shown. The cycle shown is a transcritical vapor compression
cycle because the heat rejection process occurs above CO2’s critical
pressure and consists of “gas cooling” rather than ordinary Evaporator
condensation. Presently, this cycle is being applied to commercial
refrigeration systems such as supermarkets. Figure 5: T ranscritical vapor compression refrigeration cycle components.

The fadeout vessel shown in Figure 5 limits the CO2 pressure during For all refrigeration systems using CO2, the level of water contamination
a shutdown. Located on the low-side of the system and oriented so must be kept low. The water that may be present could be liquid,
liquid may drain during operation, its volume is such that as liquid ice, and/or hydrates (crystalline solids that appear as ice). The
flashes into vapor upon warming, the pressure increase is maintained ice and hydrates form in the low-temperature side of the system,
at a modest level. Other methods include relieving the pressure particularly behind expansion devices and inside receivers, pumps,
by safety relief valves and subsequent recharge or by a small and evaporators. Currently, it is recommended that the water content
recondensation unit. be maintained at a concentration of 10 ppm (v/v) or less, preventing
formation of hydrates.8

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 CO2 – NH3 Cascade Cycle
Industrial refrigeration systems operate with significantly larger
capacities, resulting in larger component sizes for evaporators,
compressors, condensers, control valves, vessels, and piping, among
psi
3 2 others. Due to the high pressures of CO2 when above the critical
1,450 point, industrial refrigeration systems are currently designed as
1,160 subcritical cycles in which the CO2 pressure remains below the
critical pressure where manufactured components are generally
725
P
available at the working design pressure. With subcritical cycles,
the heat rejection process involves the phase change from vapor
to liquid, which is actual condensation. The focus of the remainder
290
of this article is CO2 subcritical vapor compression refrigeration
cycles as they are applied in the field of industrial refrigeration.
145 General references regarding CO2 refrigerant in industrial refrig-
4 1
eration systems include the ASHRAE Handbook – Refrigeration9
and the IIAR (International Institute of Ammonia Refrigeration)
h CO2 Handbook.8

Figure 6: p -h diagram for the transcritical compression refrigeration cycle.

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CO2 when used in subcritical vapor compression cycles appears on A cascade heat exchanger transfers the heat from the low-
the low-temperature circuit of a cascade system or as a secondary temperature circuit to the high-temperature circuit; it serves as
coolant where the highest CO2 pressure is modest. In either situation, both an evaporator and as a condenser. A favorable temperature
NH3 is confined to the machinery room with a much reduced charge. difference in the cascade condenser is needed to transfer heat
A schematic of a CO2 – NH3 cascade system is shown in Figure 7 from the CO2 to the NH3 and is typically designed between 13.3 °C
where the high-temperature circuit (5-6-7-8) uses NH3 and the (23.9 °F) and 12.2 °C (21.96 °F), balancing equipment and
low-temperature circuit uses CO2 (1-2-3-4). operating costs as shown in Figure 8.

The cascade heat exchanger is crucial in the operation of the

NH3 Condenser CO2 – NH3 cascade system. It must prevent leakage of CO2 to the
3 2 NH3 side which, if it occurs, would likely shut down the system.
Approaches to avoid shutdown of the system include: redundant
heat exchangers that may be isolated and alarming systems detecting
4 1 leaks before the system shuts down. The design pressure on the
Cascade NH3
Compressor CO2 side of the cascade heat exchanger is high – about absolute
Fadeout Condenser
Vessel 5 8 41.4 bar (600 psi). Three types of heat exchangers are suitable
CO2 Evaporator
for the cascade heat exchanger: shell-and-tube, plate-and-frame,
6 7 and shell-and-plate.
CO2
Compressor

Figure 7: C ascade vapor compression refrigeration system.

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 Shell-and-tube: This configuration is an acceptable choice, but
suffers the disadvantage of a relatively high NH3 charge and large
footprint. To reduce the risk of leakage in the tube and tube-sheet
joints, shell-and-tube heat exchangers are available with double-
3 2 tubes (concentric), providing an additional barrier to leakage.
psi
1,450 NH3
1,160 Plate-and-frame: These heat exchangers are relatively small and
need only small NH3 charges. Additionally, their configuration is
725 such that if a weld fails, the CO2 will not leak into the NH3. Because
P
5 8 of the high CO2 design pressure, fully welded construction is
∆T Cascade HE
4 1 required.
290
Shell-and-plate: A moderately low NH3 charge, small footprint,
h
CO2 and lower cost than plate-and-frame heat exchangers characterize
145 6 7
these units. The plate-stack (inside of which the CO2 condenses)
is submerged in NH3, so any leak that may occur will allow CO2
to enter the NH3 side.
h

Figure 8: Pressure-enthalpy diagram for the NH3 – CO2 cascade refrigeration system.

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If a leak were to occur on the high CO2 pressure side of the cascade
condenser, the CO2 would leak into the NH3 and chemically react 5
to form ammonium carbamate (H2NCO2NH4), which is corrosive to COP 2-st
4.5
steel and appears as a white powder precipitate. If ammonium COP CC –10°F
carbamate forms, it clogs the system, especially filters and valves. 4 COP CC 0°F

Therefore, detectors are used to instantly sense the presence of COP CC 10°F
3.5
ammonium carbamate, closing automatic isolating valves and
alerting plant personnel, so the contamination does not spread 3

throughout the system. Fortunately, ammonium carbamate can

COP
2.5
be washed out with hot water.
2

Figure 9 shows the predicted performance of an ideal CO2 – NH3 1.5 Ideal Compressor Efficiencies
cascade cycle compared to that of an ideal two-stage NH3 refrigeration Approach Temperature = 0°F
1
system. “Ideal” refers to the following conditions: saturated liquid
at exit of condenser, saturated vapor at exit of evaporator, no 0.5
pressure losses and no heat transfer in piping, and 0 °C (0 °F) 0
approach temperature for the cascade condenser. The NH3 two-stage –76 –58 –40 –22 –4 14 32
has a greater COP compared to the CO2 – NH3 cascade system Evaporating Temperature (°F)
for evaporating temperatures varying from – 28.9 °C (– 20 °F) to
– 51.1 °C (– 60 °F) for cascade condenser temperatures – 23.2 °C Figure 9: Variation of ideal NH3 two-stage cycle COP with ideal CO2 – NH3 cascade
(– 10 °F), – 17.8 °C (0 °F), and – 12.2 °C (10 °F), for 0 °C (0 °F ) cycle COP with evaporating temperature at 0°F approach temperature and different
cascade temperatures.
approach temperature.
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The influence of the cascade temperature is observed to be small.
At about – 0.6 °C (31 °F), the NH3 two-stage COP is approximately 4
10% greater than that of the CO2 – NH3 cascade and decreases to COP 2-st
3.5
about 1% greater at – 51.1 °C (– 60 °F). Figure 10 uses realistic COP CC
compressor efficiency for the NH3 two-stage and CO2 – NH3 cascade 3
systems to predict COP where the cascade temperature and cascade 2.5
approach temperatures are fixed at – 6.7 °C (20 °F) and – 4.4 °C
(8.0 °F), respectively. 2

COP
1.5
Figure 10 predicts that the CO2 – NH3 cascade COP overtakes the
1
NH3 two-stage at roughly – 42.8 °C (– 45 °F) evaporating temperature.
Operating experience reported by Toogood11 for one CO2 – NH3 0.5
cascade system used in a cold storage warehouse – 28.9 °C (– 20 °F)
0
freezer, – 6.7 °C (+20 °F) cooler and dock with blast freezing – 50 °C
–76 –58 –40 –22 –4 14 32
(– 58 °F) demonstrated reduced electrical power consumption for Evaporating Temperature (°F)
refrigeration by 5.8% compared to a two-stage NH3 system. Lynch12
has subsequently reported similar results for eleven CO2 – NH3 Figure 10: Comparison of cycle COP for NH3 two-stage with cycle COP for CO2 – NH3
cascade systems operating throughout the United States. cascade using realistic compressor efficiencies where the cascade temperature is
20 °F and the approach temperature is 8.0 °F.

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CO2 as a Secondary Coolant
CO2 used as a secondary coolant in conjunction with a vapor
compression system is shown schematically in Figure 11. In this
High-Pressure 3 2
instance, the entire refrigeration capacity is developed by the Receiver Condenser
two-stage NH3 refrigeration system, which cools the CO2 secondary
coolant in an NH3 evaporator (liquid chiller). 1 High-Stage
4 Compressor

The two-stage NH3 charge is significantly reduced because it is only Flash Tank/
needed by the evaporator, condenser, piping, and the vessels in Expansion Valve 5
Intercooler
the machinery room, except for the outside evaporative condenser. Low-Stage
6 Expansion Compressor
However, if the evaporative condenser were replaced with a cooling CO2 Process Valve
tower and heat exchanger, all the NH3 charge could reside in the Heat Exchanger 7 Surge Drum
7
machinery room. Specifically, Figure 11 shows a pumped recirculating 8
10 11 NH3 Evaporator
liquid coolant CO2 system where liquid is both supplied to the CO2 9
process heat exchanger and returned. e.g. HERMETIC Pump

Alternatively, a volatile liquid CO2 system is possible where CO2

boils in the CO2 process heat exchanger now serving as an evaporator, Figure 11: Two-stage NH3 vapor compression system with CO2 as a secondary coolant.
returning vapor (or mixture) back to the NH3 evaporator for condensing
as shown in Figure 12, where the CO2 state points 10 and 11 reveal
the CO2 liquid-to-vapor conversion. The advantage of the volatile

17
fluid is the reduced CO2 charge. Boiling in the CO2 evaporator uses
CO2’s latent heat of evaporation (330.3 kJ/kg [142 Btu/lb]) rather
than its relatively low liquid specific heat (2.1 kJ/kg·K [0.5 Btu/lb·°F]).
Thus, a volatile fluid system delivering one pound of CO2 provides
142 Btu (149 kJ) of refrigeration, converting to a vapor, while an
psi 3 2
entirely liquid system with a liquid temperature increase of 5.6 °C NH3
1,450
(10 °F) merely provides 11.6 kJ/kg CO2, or 5 Btu/lb CO2. Another 1,160
4
possibility is direct expansion in the CO2 evaporator and subsequent 8
5 1
CO2 recondensing. Combinations of the CO2 systems described P 725
10 11
above are also possible.
∆T CO2 Evaporator
6 7

Generally, lubricating oil is not present in the CO2 passing through 290

the evaporators. In this way, the greatest overall heat transfer CO2 h
coefficient is achieved, resulting in very good system performance. 145
Oil-free reciprocating compressors are available for use with CO2.
Lubricated reciprocating or screw compressors may also be used in
conjunction with oil separators using both mechanical separation h
and coalescing elements. One caution is in order: components such
as valves and controls must be able to operate oil-free. Figure 12: p-h diagram for CO2 as a volatile secondary fluid.

18
Conclusions
CO2 is one of the five natural refrigerants and over the past 20 years without drawbacks, two of which are high system working pressure
has gained popularity, particularly with low-temperature refrigeration and limited useful operating temperature range of – 53.9 °C (– 65 °F)
for industrial systems. When CO2 is used in a cascade or a secondary to 26.7 °C (80 °F). Manufacturers are adding high-pressure com-
coolant refrigeration system, the ammonia system charge is reduced ponents to their offerings, supporting the application of refrigerant
by about 80% and confined to the machinery room where the CO2. With continued good engineering design and industry support,
consequences of a leak or spill are decreased. However, CO2 is not CO2 will increase its popularity as an industrial system refrigerant.

References
1. Molina, M. J., F. S. Rowland. 1974. “Stratospheric sink for chlorofluoromethanes: Chlorine-atom catalyzed destruction of ozone.” Nature 249(5460): 810 – 812.
2. UNEP. 1990. “The Montreal Protocol on Substances that Deplete the Ozone Layer–As Adjusted and Amended by the Second Meeting.” United Nations Environment Programme.
3. UNEP. 1992. “The Montreal Protocol on Substances that Deplete the Ozone Layer–As Adjusted and Amended by the Fourth Meeting.” United Nations Environment Programme.
4. Lorentzen, G., 1989. “Method of Operating a Vapor Compression Cycle Under Trans- Or Supercritical Conditions.” European patent 0424474B2.
5. Lorentzen, G., 1993. “Revival of carbon dioxide as a refrigerant.” Int. J. Refrigeration 17(5): 292 – 301.
6. Green Retail Decisions. 2013. “Study Cites 125 Grocers Using Secondary, Cascade and Transcritical Refrigeration Systems in North America.” http://tinyurl.com/znsrgel.
7. R744.com. 2015. “Lineage Capitalizing on New Opportunities For Ammonia – CO2 Cascade.” http://tinyurl.com/zvkdqsb.
8. IIAR. 2014. The CO2 Handbook. Alexandria, Va: IIAR.
9. 2014 ASHRAE Handbook – Refrigeration.
10. 2013 ASHRAE Handbook – Fundamentals.
11. Toogood, C. 2011. “Cold energy management: Refrigerate and reduce.” Refrigerated & Frozen Foods Magazine (9).
12. Lynch, M. 2015. “US cold storage’s CO2 success proves skeptics wrong.” Accelerate – North American Edition 5(4): 24 – 29.

This article was published in ASHRAE Journal, August 2016. Copyright 2016 ASHRAE. Posted at www.ashrae.org. This article may not be copied and/or
distributed electronically or in paper form without permission of ASHRAE. For more information about ASHRAE Journal, visit www.ashrae.org.
19
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No reverse circulation line needed CO2 and PN 52 design

20
Germany USA Singapore
HERMETIC-Pumpen GmbH HERMETIC-Pumps Inc. HERMETIC-Pumps Singapore Pte. Ltd.,
www.hermetic-pumpen.com www.hermeticpumps.com www.hermetic-pumps.sg
[email protected]

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Booklet CO2 / EN / 07 / 2023

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