CO2

Refrigerant for Industrial Refrigeration

Part I - Sub-critical refrigeration cycles

Prepared by
Niels P Vestergaard
Content - Part I
Ø History
Ø Facts
Ø Refrigeration cycles with CO2
§ Transcritical
§ Subcritical
§ Cascade systems
§ DX – systems
§ Pump circulating systems
Ø CO2 compared with R717 & R134a
Ø Safety valves
Ø Oil
Ø Design pressure
Ø Why CO2
Ø Regulation
Ø Components for CO2
CO2 for Industrial refrigeration

Cooling

CO2 cooling

Climate change

Kyoto Protocol

Environment

Saving energy
History
 History
CO2 utilized as refrigerant in sub- and supercritical refrigeration systems

CO2 Compressor
Approx. 1900

The peak of utilizing

CO2 as refrigerant
Proposal to use CO2
as a refrigerant
(Alexander Twining Reinvention of CO2-
,British patent) refrigeration technology
(G. Lorentzen)

1850 1920 ----------1930 1960 1993

 History
Marine refrigerant systems registered at Lloyds in London

CO2

Source: S.A. Andersen ”Køleanlæg i skibe og på land” 1971

In 1970 S. Forbes Pearson, UK made an general view over the most common
used refrigerant used in marine refrigeration systems registered at Lloyds in
London
Facts
 CO2
(Carbon Dioxide / R744)

• Natural substance
• Refrigerant classified as non-toxic and non- flammable fluid
• Concentration in the atmospheric air approx. 0,04% (volume)
Refrigeration
cycles with
CO2
 Log p,h-Diagram of CO2

CO2 look like all the other

refrigerants, but …….
 CO2 Phases
1000

Pressure (bar)

Liquid Supercritical

100
73.6 bar

Critical point
Solid

10

5.2 bar Triple point Vapour

1
-80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100
Tempe rature (Deg.C)

- 56.6 Deg.C 31. Deg.C

 Log p,h-Diagram of CO2
Pressure (bar) +31 Deg.C
100
Supercritical Critical
73,6
point
Liquid

Solid -Liquid
Liquid - vapour
10
Solid Triple
5,2
- 56,6 Deg.C (freezing)
point

Solid - Vapour vapour

- 78,4 Deg.C
1
-200 -100 0 100 200 300 400 500
Enthalpy (J)
 CO2 properties compared with various refrigerants

Refrigerant R134a R404a NH3 CO2

Natural substance NO NO YES YES
Ozone Depletion Potential (ODP) * 0 0 0 0
Global Warming Potential (GWP) * 1300 3260 - 1
Critical pressure in bar 40.7 37.3 113 73.6
°C 101.2 72 132.4 31.1
Triple point in bar 0.004 0.028 0.06 5.18
°C -103 -100 -77.7 -56.6
Flammable or explosive NO NO (YES) NO
Toxic NO NO YES NO

* prEN 378-1 (2003)

Subcritical refrigeration proces
Example –10/35 bar

35 bar (0 Deg.C)

10 bar (-40 Deg.C)

Subcritical refrigeration proces
Example –10/65 bar

65 bar (25 Deg.C)

10 bar (-40 Deg.C)

 Transcritical
(supercritical)
refrigeration
process
Supercritical refrigeration process

90 bar

26,5 bar (-10 Deg.C)

Supercritical refrigeration process
Gas cooling

35 Deg.C Gas cooling 95 Deg.C

90 bar

26,5 bar (-10 Deg.C)

Residential CO2 heatpump
application for hot water
production
CO2 Automotive
aircondition application
 Supercritical refrigeration proces
Influence of compressor outlet pressure
35 oC
100 bar
90 bar
80 bar

3 Max ∆hEVAP ∆hComp-is

100 bar,COP = 2,46
2,5
COP

2 90 bar,COP = 2,51

1,5
80 bar,COP = 1,72
1
70 75 80 85 90 95 100 105 110
Compressor outlet pressure [bar]
COP = (∆hEVAP*m )/ (∆hComp-is*m)
Supercritical CO2 heat pumps
Patents:
A number of patents has to be taken into
consideration
Sub critical refrigeration
process, e.g.
• Cascade system
• DX systems
• Pump circulating systems
 +30 Deg.C Principal diagram
717 - CO2 cascade system

R717

Pressure
R717

CO2-R717 Heat exchanger

-20 Deg.C +30 Deg.C (12 bar)
-15 Deg.C
CO2 compressor -20 Deg.C (1,9 bar)

Enthalpy
-40 Deg.C
CO2-receiver
CO2

Pressure
-15 Deg.C (23 bar)
CO2
-40 Deg.C (10 bar)

-40 Deg.C
CO2-evaporator Enthalpy
 Principal diagram
+30 Deg.C
717 - CO2 brine system

R717

Pressure
R717
CO2-R717 Heat exchanger
-45 Deg.C +30 Deg.C (12 bar)
-40 Deg.C

-45 Deg.C (0,5 bar)

Enthalpy
-40 Deg.C
CO2-receiver
CO2

Pressure
CO2
-40 Deg.C (10 bar)
-40 Deg.C

CO2-evaporator Enthalpy
 +30 Deg.C Principal diagram
717 - CO2 cascade system with CO2
hot gas defrosting
R717

Pressure
R717
CO2-R717 Heat exchanger
-20 Deg.C +30 Deg.C (12 bar)
-15 Deg.C
CO2 compressor -20 Deg.C (1,9 bar)

Enthalpy
-40 Deg.C
CO2-receiver CO2 defrost
compressor CO2 +8 Deg.C (43 bar)

Pressure
-15 Deg.C (23 bar)
CO2
-40 Deg.C (10 bar)

+8 Deg.C

-40 Deg.C
CO2-evaporator Enthalpy
Principal diagram CO2 cascade system with 2
temperature levels (e.g supermarket refrigeration)
+30 Deg.C

R717,R404, R134a,….

-12 Deg.C
-7 Deg.C

-7 Deg.C
CO2

Pump circulating system

-20 Deg.C

DX system
 CO2 application
CO2 compared with R134a and R717
 Wet reurn

Wet return / Liquid lines

Liquid

Refrigerant R134a R717 CO2

Wet return line Capacity [kW] 250 250 250
∆T [K] 1 1 1
∆p [bar] 0,0263 0,0375 0,3660
Velocity [m/s] 12,6 23,0 9,4

Diameter [mm] 202 125 65

Area [mm2] 31941 12213 3310 CO2
Liquid line Velocity [m/s] 0,8 0,8 0,8 Small
pipe
diameter!

Diameter [mm] 61 36 58
Area [mm2] 2968 998 2609

Leqv = 50 [m]
Pump circ.: ncirc = 3
Evaporating temp.: TE = -40 [Deg.C]
 Wet reurn

Wet return / Liquid lines

Liquid

Refrigerant R134a R717 CO2

Wet return line Capacity [kW] 250 250 250
∆T [K] 1 1 1
∆p [bar] 0,0263 0,0375 0,3660
Velocity [m/s] 12,6 23,0 9,4
Area [mm2] 31941 12213 3310
Liquid line Velocity [m/s] 0,8 0,8 0,8
Area [mm2] 2968 998 2609

Area - R134a Area -

R717 Area - CO2 CO2
Liquid Liquid
Liquid
line line Liquid
line
9% 8%
44%
fraction is
Area -
Area - Wet high
Wet Area -
return
return Wet
line
line return
56%
91% line
92%

Leqv = 50 [m]
Pump circ.: ncirc = 3
Evaporating temp.: TE = -40 [Deg.C]
 Dry suction

Liquid
Dry suction / Liquid lines

Refrigerant R134a R717 CO2

Dry suction line Capacity [kW] 250 250 250
∆T [K] 1 1 1
∆p [bar] 0,0261 0,0375 0,3663
Velocity [m/s] 23,3 42,9 17,6

Diameter [mm] 157 95 50

Area [mm2] 19413 7075 1956 CO2
Liquid line Velocity [m/s] 0,8 0,8 0,8 Small
pipe
diameter!

Diameter [mm] 37 21 35
Area [mm2] 1089 353 975

Leqv = 50 [m]
Evaporating temp.: TE = -40 [Deg.C]
Condensing temp.: TC = -15 [Deg.C]
 Dry suction

Liquid
Dry suction / Liquid lines

Refrigerant R134a R717 CO2

Dry suction line Capacity [kW] 250 250 250
∆T [K] 1 1 1
∆p [bar] 0,0261 0,0375 0,3663
Velocity [m/s] 23,3 42,9 17,6
Area [mm2] 19413 7075 1956
Liquid line Velocity [m/s] 0,8 0,8 0,8
Area [mm2] 1089 353 975

Area -
Liquid
R134 Area -
Liquid
R717 CO2 CO2
Area -
line line Liquid Liquid
5% 5% line
Area - Area -
33% Area - fraction is
Dry Dry Dry high
suction suction suction
line line line
95% 95% 67%

Leqv = 50 [m]
Evaporating temp.: TE = -40 [Deg.C]
Condensing temp.: TC = -15 [Deg.C]
 Compressor

Compressor capacity

Refrigerant R134a R717 CO2

Capacity [kW] 250 250 250
Compressor capacity [m3/h] 1628 1092 124
Compressor capacity relative [-] 13,1 8,8 1,0

CO2
Compressors
have high
capacity

Evaporating temp.: TE = -40 [Deg.C]

Condensing temp.: TC = -15 [Deg.C]
 Liquid pump
Pumpe

Refrigerant R134a R717 CO2

High "h" [m] 3 3 3
Pump inlet pressure - ∆p [bar] 0,418 0,203 0,329
Pump inlet pressure - ∆t [oC] 14,91 5,21 0,88

CO2
Sub cooling (∆t)
is small

Pump
 log
10000
Density - R134a - R717 - CO2
CO2
Density difference
1000 between liquid and
vapour is small

100 CO2 Vapour [m3/kg]

[kg/m3]

CO2 Liquid [m3/kg]

10
R134a Vapour [m3/kg]

R134a Liquid [m3/kg]

1
R717 Vapour [m3/kg]

R717 Liquid [m3/kg]

0,1
-50 -40 -30 -20 -10 0 10 20 30 40
o
Temperature [ C]
 Density - CO2

1400

1200

1000 CO2 Liquid

800
[kg/m ]
3

600

400

200 CO2 Vapour

0
-50 -40 -30 -20 -10 0 10 20 30 40

Temperature [Deg.C]
 Difference between liquid and vapour density
1500
CO2
Liquid-
vapour
1300 [m3/kg]
R134a
Liquid-
1100 vapour
[m3/kg]
R717
Liquid-
900 vapour
F
[kg/m3]

[m3/kg] Vapour

700
liquid

500

F = ( density liquid – density vapour)

300

100
-50 -40 -30 -20 -10 0 10 20 30 40
o
temperature [ C]
 SUMMARY
CO2 application:
• Pipe dimensions in CO2 systems are small
• Due to very small vapour volume, CO2 systems are very
dynamic
• Liquid pumps in CO2 systems are sensitive to capacity
changes (low sub cooling & gas bobbles are difficult to
get rid of at high temperatures.)
• Compressors with big capacity steps can create
problems (small vapour volume).

• Frequency converters are an obvious possibility !

Safety valves
 CO2
Safety valves +31 Deg.C
Pressure (bar)

100
Supercritical Safety valve 50 bar
73,6
vapour

Liquid Safety valve 35 bar

vapour
Safety valve 20 bar
liquid

Solid -Liquid
Liquid - vapour Safety valve 35 bar

10 Safety valve 20 bar 0% solid CO2 at the

liquid triple point
Solid
78% solid CO2 at - 56,6 Deg.C
5,2 the triple point

Safety valve 50 bar

Solid - Vapour 5% solid CO2 at the

triple point
vapour
- 78,4 Deg.C
1
-200 -100 0 100 200 300 400 500
Enthalpy (J)
 Design
pressure
Design pressure is depending of:

• Pressure during operation

• Pressure during ”stand still”:
• Temperature requrements for
defrosting
• Pressure tolerances for safety
valves (10 – 15 %)
 Controlling the
pressure during
”stand still”
R717

Saturated pressure CO2

CO2
 CO2

60

55

50
Design pressure (bar-g): Ps + 15 %
Pressure (bar)

45 PS 50

40
Ps + 10% (bar-g)
35 PS 40

30
"Saturated"pressure (bar-a)

25
PS 25
20
-30 -20 -10 0 10 20
Design temperature (Deg.C)
 Design pressure

Practical limit: PS ≥ Psaturated +15%

Design pressure
Pressure peaks 5%

Safety valve 10%

Saturated pressure
CO2 and oil
 CO2 and oil Common used oil type in CO2 systems

Oil type PAO POE

Polyalfaolefin Polyol Ester Oil
(Synthetic Mineral Oil)

Solubility Low (immiscible) High (miscible)

Hydrolysis Low High affinity to water

Oil separation system § Special demand: § No special requirements

§ High filtration demanded (system requirements like HCFC / HFC )
§ Multistage coalescing filters
§ Active carbon filter
Oil return system § Special demand: § Simple
§ Oil drain from low temperature (system requirements like HCFC / HFC )
receiver ( oil density lower than
CO2 -opposite NH3)
Challenge § Oil separation and return § High affinity to water
system § Long term stability of oil
§ Long term oil accumulation in § ”Clean” refrigerant system required
e.g. evaporators
Why CO2 ?
Refrigeration and Air Conditioning
Household Commercial/ Industrial Petro-
Compressors Supermarket Refrigeration Chemical

Appliance
Controls SVA-HS

R600a R134a R410 R717 R1270

CO2
• Small valves made of
e.g. brass, copper
• Valves are NOT
applicable for Ammonia
• Large quantity
•
•
•
•
Danfoss Industrial
Refrigeration A/S
All valves are suitable for Ammonia
All valves are in steel
”Big” valves in small quantity
Requirements for type approvals,
traceability etc.
 Why CO2 ?
Commercial/ Industrial
CO2 – Drivers Supermarket Refrigeration

E
Environment
Phase out CFC, HCFC: Change to CO2
(ODP (Ozone Depletion Potential), GWP (Global Warming Potential) )

Safety
Increased restrictions on toxic/flammable refrigerants (e.g.
requirements for systems with big R717 charge)
E
Cost
• Reduced running cost due to increased
efficiency (compressor efficiency, heat transfer)
• Reduced cost on refrigerants.
E E
• Reduced size on components.
 CO2
components
for industrial
refrigeration
High pressure components - CO2
 CO2
Refrigerant for Industrial Refrigeration
Part II - Properties, compatibility & chemical reactions

Prepared by
Finn Broesby Olsen &
Niels P Vestergaard
Content - Part II
Ø Safety aspects with CO2
Ø Chemical reaction with water and other impurities in CO2 systems
Ø Removing water from CO2 systems
§ Filter driers
Ø Water (moisture) in CO2 systems
§ Solubility
§ Moisture indicators
§ Cascade systems
Ø How can water penetrate into CO2 systems
Ø Compatibility with metal, elastomere
Safety aspects
with CO2
 CO2
(Carbon Dioxide / R744)

• Natural substance
• Refrigerant classified as non-toxic and non- flammable fluid
• Concentration in the atmospheric air approx. 0,04% (volume)
Safety Aspects of CO2
Carbon dioxide replaces air, and causes lack of oxygen. At presence of sufficient oxygen, CO2 has a narcotic effect at stronger
concentration. With smaller amounts, CO2 has a stimulating effect on the respiratory center. Due to the acidic characteristics of CO2, a
certain local irritating can appear, particularly on the mucous membrane of nose, throat and eyes as well as induce coughing. The symptoms
associated with the inhalation of air containing carbon dioxide are, with increasing carbon dioxide concentrations.
The data, valued for adults with good health, are as follows:

§ 0,04% Concentration in the atmospheric air

§ 2% 50% increase in breathing rate

§ 3% 10 Minutes short term exposure limit; 100% increase in breathing rate

§ 5% 300% increase in breathing rate, headache and sweating may begin after about an hour
(Com.: this will tolerated by most persons, but it is physical burdening)

§ 8% Short time exposure limit

§ 8-10% Headache after 10 or 15 minutes. Dizziness, buzzing in the ears,blood pressure increase,
high pulse rate, excitation, and nausea.

§ 10-18% After a few minutes, cramps similar to epileptic fits, loss of con-sciousness, and shock
(i.e.; a sharp drop in blood pressure) The victims recover very quickly in fresh air.

§ 18-20% Symptoms similar those of a stroke.

(source: AGA Gas Handbook)

 Chemical reaction with
water and other impurities
in CO2 systems
Water in CO2 systems

If water is
present in CO2
systems, water
reacts with CO2
and creates
Carbonic acid.

The
concentration is
depending on
the water content

Strong acid
 Water in CO2 systems
Heavy corrosion in a steel
pipe from a CO2 system
caused by Carbonic acid.
Corrosion will not take place
in a well maintained CO2
refrigeration system.

X-ray defraction:
Crystal structure analysis of
the steel pipe.
 Water in CO2 systems

CO2 gas hydrate - CO2(H2O)8

With very high

concentration of water in
CO2 systems, the CO2
gas hydrate can be
performed. CO2 gas
hydrate looks like ice,
but exists also at higher
temperatures
The CO2 gas hydrate can
create problems in e.g.
filters
 Ammonia in CO2 systems

• The solid substance Ammonium Carbamate is formed immediately if

CO2 gets in contact with ammonia.
• Ammonium Carbamate is a corrosive substance (white powder)
• Ammonium Carbamate will dissolve, if it is heating up to a temperature
higher than approx. 60 Deg. C
 PAO Polyalfaolefin Oil in CO2 systems
(Synthetic Mineral Oil)

• If oxygen is present in CO2 system, it will react with the PAO oil
•Oxygen can be present e.g. from corrosion in tubes
• Organic Acid and Water are generated
• The Organic Acids from oxidation are relatively strong acids
PEO Polyol Ester Oil in CO2 systems

• If water is present in CO2 system, it will react with Ester oil

•Organic Acid and Alcohol are generated
• The Organic Acid is relative weak acid
Removing water from CO2
systems
 Filter drier in CO2 systems

Desiccant core absorbing

Filter mat collecting solid
water from refrigerant
contaminants
(Molecular Sieves)
 Molecular Sieves in CO2 systems
Refrigerant
molecules and
micropore size
in Zeolite LTA

CO2 penetrates through the micropores unlike other refrigerants like

R134a. If water is present, it will also penetrate through the micropores
and throw CO2 out, due to difference in polarity of water and CO2.
CO2 driers with Molecular Sieves are very efficient.
Molecular Sieves water uptake in CO2 systems
 Molecular Sieves water uptake
CO2 /R134a systems

CO2 R134a

The efficiency of the molecular sieves with CO2 and R134a are almost identical
Water (moisture) in CO2
 Water Solubility in Refrigerants. Water Solubility in Refrigerants.
Gas Phase Liquid Phase
(Y-Axis Linear) (Y-Axis Linear)

1600
2500

1400

2000
mg of water/kg of refrigerant [ppm]

1200

mg of water/kg refrigerant [ppm]

R134a R134a
1000
1500

800
CO2
600 1000

400
500
200

0
CO2 0
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
Temperature [ oC] Tem perature [ oC]
m g of wa ter/k g of re frige rant [ppm ]
100
90 CO2 + CO2
80
70
CO2 + Water
60 ICE
50
40 Water Solubility in Refrigerants. Gas Phase
30
20 (Y-Axis Linear)
10 CO2 + H20 gas Phase
0
-50 -40 -30 -20 -10 0 10 20
Temperature [oC]

1600
NH3 R134a
1400
mg of water/kg of refrigerant [ppm]

1200
R22
1000

800

600 R404A

400

200
CO2
0
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
o
Temperature [ C]
 Water in CO2 systems

Danfoss Sight Glass SGN in CO2

100
”Wet”
90
mg of water/kg refrigerant [ppm]

80
70
60
50
40
30
”Dry”
20
10
0
-50 -40 -30 -20 -10 0 10 20
Tem perature [oC]
 CO2 system with filter drier and indicator

Evaporator Condenser

Filter drier Moisture indicator

 Water in CO2 systems

How can water penetrate into a CO2 system?

ØThe pressure of CO2 systems is always above the atmospheric
pressure; therefore there are not the same risks, as e.g. in NH3
systems, that air / water penetration into a leaking CO2 system,
however permeation of water into the system is still possible.
Ø When charging CO2, there are different specifications of CO2. Some
of them allow relative high amounts of water.

ØCO2 is treated as a very safe refrigerant, and is therefore handled

without following the normal safety requirements. If a system is
opened up, air can penetrate into it, and the moisture can condense
inside the tubes. If the system is not evacuated properly, some water
may well be retained.

ØBy charging lubricant (oil) to the compressor.

ØBy decomposition of oil

 CO2 compatibility with metal and polymers
Ø CO2 is compatible with almost all common metallic materials, unlike
NH3. There are no restrictions from a compatibility point of view, when
using copper or brass.

Ø The compatibility of CO2 and polymers is much more complex. Because

CO2 is a very inert and stable substance, the chemical reaction with
polymers is not critical.

Ø The main concern with CO2 is the physiochemical

effects, such as permeation, swelling and the generation of cavities and
internal fractures. These effects are connected with the solubility and
diffusivity of CO2 in the actual material.
 CO2 compatibility with metal and polymers
Ø The compatibility of CO2 and polymers can be sensitive.

Ø CO2 penetrates into polymers, but has difficulties to get out fast.

Ø CO2 pressure, temperature and pressure change are important factors

But !

Ø In sub-critical CO2 refrigeration the pressure is relative low (< 50 bar)

and further more pressure changes take place relative slow.
Experience has shown that standard CR O-rings can be used with CO2,
under these conditions.
 SUMMARY

Ø CO2 is a natural non-toxic/non-flammable substance

Ø CO2 is a relative unreactive refrigerant

Ø All reaction involving CO2 need water to take place.

Ø The acceptable water content in CO2 systems is much lower

than in other refrigeration systems

Ø Water, oxygen, oxides, oil, contaminants and system metals

are the most important chemical reactants. Also in systems
with CO2.
 Thank you
for attention!
Questions ?