CO2

Refrigerant for Industrial Refrigeration

Part I - Sub-critical refrigeration cycles

Prepared by Niels P Vestergaard

Content - Part I
History Facts Refrigeration cycles with CO2 Transcritical Subcritical Cascade systems DX systems Pump circulating systems CO2 compared with R717 & R134a Safety valves Oil Design pressure Why CO2 Regulation 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 ,British patent) Reinvention of CO2refrigeration technology (G. Lorentzen)

1850

1920 ----------1930

1960

1993

History
Marine refrigerant systems registered at Lloyds in London

CO2

Source: S.A. Andersen Kleanlg i skibe og p 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 73,6

Supercritical Liquid

Critical point

Solid -Liquid
10

Liquid - vapour

Solid
5,2 - 56,6 Deg.C

Triple (freezing) point

vapour

Solid - Vapour
- 78,4 Deg.C

1 -200

-100

100

200

300

400

500

Enthalpy (J)

CO2 properties compared with various refrigerants

Refrigerant Natural substance Ozone Depletion Potential (ODP) * Global Warming Potential (GWP) * Critical pressure in Triple point in Flammable or explosive Toxic
* prEN 378-1 (2003)

R134a NO 0 1300 40.7 101.2 0.004 -103 NO NO

R404a NO 0 3260 37.3 72 0.028 -100 NO NO

NH3 YES 0 113 132.4 0.06 -77.7 (YES) YES

CO2 YES 0 1 73.6 31.1 5.18 -56.6 NO NO

bar C bar C

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 90 bar Gas cooling 95 Deg.C

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 2,5 COP 2 1,5

Max
100 bar,COP = 2,46 90 bar,COP = 2,51

hEVAP

hComp-is

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

R717
CO2-R717 Heat exchanger
-20 Deg.C -15 Deg.C

Pressure

+30 Deg.C (12 bar)

CO2 compressor

-20 Deg.C (1,9 bar)

Enthalpy -40 Deg.C

CO2-receiver
Pressure

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

CO2

-40 Deg.C

CO2-evaporator

Enthalpy

Principal diagram
+30 Deg.C

717 - CO2 brine system

R717

R717
CO2-R717 Heat exchanger
-45 Deg.C -40 Deg.C

Pressure

+30 Deg.C (12 bar)

-45 Deg.C (0,5 bar)

Enthalpy -40 Deg.C

CO2-receiver
Pressure

CO2

CO2
-40 Deg.C

-40 Deg.C (10 bar)

CO2-evaporator

Enthalpy

+30 Deg.C

Principal diagram 717 - CO2 cascade system with CO2 hot gas defrosting
Pressure

R717

R717
CO2-R717 Heat exchanger
-20 Deg.C -15 Deg.C

+30 Deg.C (12 bar)

CO2 compressor

-20 Deg.C (1,9 bar)

Enthalpy -40 Deg.C

CO2-receiver

CO2 defrost compressor

Pressure

CO2

+8 Deg.C (43 bar) -15 Deg.C (23 bar) -40 Deg.C (10 bar)

CO2

+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 Wet return line Capacity T p Velocity

[kW] [K] [bar] [m/s]

R134a 250 1 0,0263 12,6

R717 250 1 0,0375 23,0

CO2 250 1 0,3660 9,4

Diameter Area Liquid line

Velocity

[mm] [mm2] [m/s]

202
31941 0,8

125
12213 0,8

65
3310 0,8

CO2
Small pipe diameter!

Diameter Area

[mm] [mm2]

61
2968

36
998

58
2609

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

Wet reurn

Wet return / Liquid lines

Liquid

Refrigerant Wet return line Capacity T p Velocity Area Liquid line Velocity Area
Area Liquid line 9%

R134a
[kW] [K] [bar] [m/s] [mm2] [m/s] [mm2]

R717 250 1 0,0375 23,0 12213 0,8 998

Area Liquid line 44%

CO2 250 1 0,3660 9,4 3310 0,8 2609

CO2

250 1 0,0263 12,6 31941 0,8 2968

R134a

Area Liquid line 8% Area Wet return line 91%

R717

CO2
Area Wet return line 56%

Area Wet return line 92%

Liquid fraction is high

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

Dry suction Liquid

Dry suction / Liquid lines

Refrigerant R134a
[kW] [K] [bar] [m/s]

R717 250 1 0,0375 42,9

CO2 250 1 0,3663 17,6

Dry suction line

Capacity T p Velocity

250 1 0,0261 23,3

Diameter Area Liquid line Velocity

[mm] [mm2] [m/s]

157 19413 0,8

95 7075 0,8

50 1956 0,8

CO2
Small pipe diameter!

Diameter Area

[mm] [mm2]

37 1089

21 353

35 975

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

Dry suction Liquid

Dry suction / Liquid lines

Refrigerant R134a
[kW] [K] [bar] [m/s] [mm2] [m/s] [mm2]

R717 250 1 0,0375 42,9 7075 0,8 353

CO2 250 1 0,3663 17,6 1956 0,8 975

Dry suction line

Capacity T p Velocity Area

250 1 0,0261 23,3 19413 0,8 1089

Liquid line

Velocity Area

Area Liquid line 5%

R134

Area Liquid line 5% Area Dry suction line 95%

R717
Area Liquid line 33%

CO2

CO2
Area Dry suction line 67%

Area Dry suction line 95%

Liquid fraction is high

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

Compressor

Compressor capacity
Refrigerant Capacity Compressor capacity Compressor capacity relative
[kW] [m3/h] [-]

R134a 250 1628 13,1

R717 250 1092 8,8

CO2 250 124 1,0

CO2
Compressors have high capacity

Evaporating temp.: TE = -40 [Deg.C] Condensing temp.: TC = -15 [Deg.C]

Liquid pump
Pumpe

Refrigerant High "h" Pump inlet pressure - p Pump inlet pressure - t [m] [bar] [oC]

R134a 3 0,418 14,91

R717 3 0,203 5,21

CO2 3 0,329 0,88

CO2
Sub cooling (t) is small

Pump

log
10000

Density - R134a - R717 - CO2

CO2
1000

Density difference between liquid and vapour is small

100 [kg/m3]

CO2 Vapour [m3/kg] CO2 Liquid [m3/kg]

10

R134a Vapour [m3/kg] R134a Liquid [m3/kg]

R717 Vapour [m3/kg] R717 Liquid [m3/kg]

0,1 -50 -40 -30 -20 -10 0
o

10

20

30

40

Temperature [ C]

Density - CO2
1400

1200

1000

CO2 Liquid

[kg/m ]

800

600

400

200

CO2 Vapour

0 -50

-40

-30

-20

-10

10

20

30

40

Temperature [Deg.C]

Difference between liquid and vapour density

1500 CO2 Liquidvapour [m3/kg] R134a Liquidvapour [m3/kg] R717 Liquidvapour [m3/kg]

1300

1100

[kg/m3]

900

Vapour

700

liquid
500

F = ( density liquid density vapour)

300

100 -50 -40 -30 -20 -10 0 o temperature [ C] 10 20 30 40

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
Pressure (bar)

Safety valves
100 73,6

+31 Deg.C
Safety valve 50 bar vapour Safety valve 35 bar vapour

Supercritical Liquid
Safety valve 20 bar liquid

Solid -Liquid
10
Safety valve 20 bar liquid

Liquid - vapour

Safety valve 35 bar

0% solid CO2 at
triple point

the

Solid
5,2

78% solid CO2 at

the triple point

- 56,6 Deg.C
Safety valve 50 bar

Solid - Vapour
- 78,4 Deg.C

5% solid CO2 at
triple point

the

vapour
200 300 400 500

1 -200

-100

100

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 %)

R717

Controlling the pressure during stand still

Saturated pressure CO2

CO2

CO2
60 55 50 Pressure (bar)
Design pressure (bar-g): Ps + 15 %

45 40 35 30 25

PS 50

PS 40

Ps + 10% (bar-g)

"Saturated"pressure (bar-a)

PS 25

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

Design pressure
Practical limit: PS Psaturated +15% Design pressure Pressure peaks Safety valve
5% 10%

Saturated pressure

CO2 and oil

CO2 and oil

Oil type

Common used oil type in CO2 systems

PAO
Polyalfaolefin
(Synthetic Mineral Oil)

POE
Polyol Ester Oil
High (miscible)

Solubility

Low (immiscible)

Hydrolysis

Low

High affinity to water

Oil separation system

Special demand: High filtration demanded

Multistage coalescing filters Active carbon filter

No special requirements
(system requirements like HCFC / HFC )

Oil return system

Special demand: Oil drain from low temperature receiver ( oil density lower than CO2 -opposite NH3) Oil separation and return system Long term oil accumulation in e.g. evaporators

Simple
(system requirements like HCFC / HFC )

Challenge

High affinity to water Long term stability of oil Clean refrigerant system required

Why CO2 ?

Refrigeration and Air Conditioning

Household Compressors Commercial/ Supermarket Industrial Refrigeration PetroChemical

Appliance Controls

SVA-HS

R600a

R134a

R410

R717
Danfoss Industrial Refrigeration A/S

R1270

Small valves made of e.g. brass, copper Valves are NOT applicable for Ammonia Large quantity

CO2

All valves are suitable for Ammonia All valves are in steel Big valves in small quantity Requirements for type approvals, traceability etc.

Why CO2 ?
CO2 Drivers
Environment
Phase out CFC, HCFC: Change to CO2
(ODP (Ozone Depletion Potential), GWP (Global Warming Potential) ) Commercial/ Supermarket Industrial Refrigeration

E E E E

Safety
Increased restrictions on toxic/flammable refrigerants (e.g. requirements for systems with big R717 charge)

Cost
Reduced running cost due to increased efficiency (compressor efficiency, heat transfer) Reduced cost on refrigerants. 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
Safety aspects with CO2 Chemical reaction with water and other impurities in CO2 systems Removing water from CO2 systems Filter driers Solubility Moisture indicators Cascade systems How can water penetrate into CO2 systems Compatibility with metal, elastomere Water (moisture) in CO2 systems

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% 2% 3% 5% 8% 8-10%

Concentration in the atmospheric air

50% increase in breathing rate 10 Minutes short term exposure limit; 100% increase in breathing rate 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) Short time exposure limit 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 water from refrigerant (Molecular Sieves)

Filter mat collecting solid contaminants

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. Gas Phase

(Y-Axis Linear)
1600

Water Solubility in Refrigerants. Liquid Phase

(Y-Axis Linear)

2500

1400 mg of water/kg of refrigerant [ppm]

mg of water/kg refrigerant [ppm]

1200

2000

R134a
1000 800

R134a
1500

CO2

600

1000

400

500

200

0 -60

CO2
-50 -40 -30 -20 -10 0 10 20 30 40 50 60 Temperature [ oC]

0 -60 -50 -40 -30 -20 -10 0 10 [ oC] 20 30 40 50 60 Tem perature

m g of wa ter/k g of re frige rant [ppm ]

100 90 80 70 60 50 40 30 20 10 0 -50

CO2 + ICE

CO2 + Water

CO2

Water Solubility in Refrigerants. Gas Phase

(Y-Axis Linear)

CO2 + H20 gas Phase

-40 -30 -20 -10 0 10 20 Temperature [oC]

1600

NH3
mg of water/kg of refrigerant [ppm] 1400 1200 1000 800 600 400 200 0 -60 -50 -40 -30 -20 -10 0
o

R134a R22

R404A

CO2
10 20 30 40 50 60 Temperature [ C]

Water in CO2 systems

Danfoss Sight Glass SGN in CO2
100 mg of water/kg refrigerant [ppm] 90 80 70 60 50 40 30
Dry

Wet

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?
The 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.
When charging CO2, there are different specifications of CO2. Some of them allow relative high amounts of water. CO2 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. By charging lubricant (oil) to the compressor. By decomposition of oil

CO2 compatibility with metal and polymers

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. 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. 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

The compatibility of CO2 and polymers can be sensitive. CO2 penetrates into polymers, but has difficulties to get out fast. CO2 pressure, temperature and pressure change are important factors

But ! 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
CO2 is a natural non-toxic/non-flammable substance CO2 is a relative unreactive refrigerant All reaction involving CO2 need water to take place. The acceptable water content in CO2 systems is much lower than in other refrigeration systems Water, oxygen, oxides, oil, contaminants and system metals are the most important chemical reactants. Also in systems with CO2.

Thank you for attention!

Questions ?