Refrigeration and Air Conditioning Controls

Article

CO 2 Refrigerant for Industrial Refrigeration

R E F R I G E R AT I O N A N D A I R C O N D I T I O N I N G

Article

CO2 - Refrigerant for Industrial Refrigeration

Contents

Page Introduction .................................................................................................................................. 3 CO2 as a refrigerant ..................................................................................................................... 4 CO2 as a refrigerant in industrial systems ................................................................................... 6 Design pressure .......................................................................................................................... 7 Efficiency ..................................................................................................................................... 8 Oil in CO2 systems ....................................................................................................................... 8 Component size .......................................................................................................................... 8 Refrigerant charge in CO2-NH3 cascade systems ...................................................................... 9 Material compatibility ................................................................................................................. 10 Water in CO2 systems ................................................................................................................ 10 Leaks in CO2-NH3 cascade systems ......................................................................................... 12 Safety valves in CO2 systems .................................................................................................... 12 Safety ......................................................................................................................................... 13 Conclusion ................................................................................................................................ 13 Danfoss valves and controls for CO2 ......................................................................................... 14

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CO2 - Refrigerant for Industrial Refrigeration

Introduction

The application of carbon dioxide (CO2) refrigeration systems is not new. Carbon dioxide was first proposed as a refrigerant by Alexander Twining [1], who mentioned it in his British patent in 1850. Thaddeus S.C. Lowe experimented with CO2 military balloons, but he also designed an ice machine with CO2 in 1867. Lowe also developed a machine onboard a ship for transportation of frozen meat. From reading the literature it can be seen that CO2 refrigerant systems were developed during the following years and they were at their peak in the 1920's and early 1930's. CO2 was generally the preferred choice for use on board ships whilst ammonia (NH3 or R717) was more common in land applications [2]. With the advent of the "Freon" refrigerants initially R12, the application of CO2 lessened. The main reason for its decline was certainly the rapid loss of capacity and pressure increase at high temperatures. Ammonia has continued to be the dominant refrigerant for industrial refrigeration applications over the years.

In the 1990's there was renewed focus of the advantages offered by using CO2, due to ODP (Ozone Depletion Potential) and GWP (Global Warming Potential), which has restricted the use of CFC's and HFC's and restrictions on the refrigerant charge in large ammonia systems. CO2 belongs to the so-called "Natural" refrigerants, together with e.g. ammonia, hydrocarbons such as propane and butane, and water. All of these refrigerants have their respective disadvantages: Ammonia is toxic, hydrocarbons are flammable, and water has limited application possibilities. In comparison, CO2 is non-toxic and nonflammable, but has a double role in the environment. CO2 is necessary for all life on earth, but is also a green house gas, which can change the environment if its concentration in the atmosphere changes.

[1] Bondinus, William S [2] Lorentzen, Gustav

ASHRAE Journal April 1999 Reprint from IIR Conference 1994 Proceedings "New Applications of Natural Working Fluids in Refrigeration and Air Conditioning"

Danfoss A/S (RC-CM / MWA), 12 - 2002

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CO2 - Refrigerant for Industrial Refrigeration

CO2 as a refrigerant

Characteristics of CO2 The pressure-enthalpy diagram for CO2 is shown in fig 1. The pressure-temperature diagram for CO2 is shown in fig 2. Thermodynamic properties of CO2 seem to be similar to many other common refrigerants, but there are some exceptions: The triple point for CO2 is much higher than for all other common refrigerants (see table 1). In the pressure-enthalpy diagram (see fig 1), the triple point is actually a line at a pressure of 5.18 bar, and a temperature of 56.6C. In the triple point, an equilibrium of CO2 vapour, liquid and solid exists.

The critical pressure of CO2 is 73.6 bar, and the critical temperature is + 31C. In the supercritical phase, CO2 has properties which are almost similar to a high-density vapour.
NH3 CO2 Pressure Temperature Pressure Temperature Triple point 5.18 bar Critical pressure 73.6 bar 56.6C (31C) 0.06 bar 113 bar 77.7C (132C)

Table 1: Triple points for CO2 and NH3

CO2
Pressure (bar)
100 73.6

+31C

Supercritical Liquid

Solid - Liquid
10

Liquid - Vapour

Solid
5.2 - 56.6C

Solid - Vapour
- 78.4C

Vapour

1 -200

-100

100

200

300

400

500 Enthalpy(J)

Fig. 1 The pressure-enthalpy diagram for CO2

CO2 Phases
1000

Pressure (bar)

Liquid

Supercritical

100

Note: CO2 is a unique substance used for many different purposes in other industries. E.g. - By increasing pressure, CO2 becomes a solvent. This is utilized in extraction of one substance from another, and for cleaning processes. - CO2 solid can be used as a substitute for sand in "sandblasting". - Fire fighting systems

Solid
10

Triple point

Vapour

1 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100

Temperature (C)

Fig. 2 Pressure-temperature diagram for CO2

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CO2 - Refrigerant for Industrial Refrigeration

CO2 as a refrigerant (cont.)

The high-saturated pressure at ambient temperature is often the first barrier that needs to be considered when proposing CO2 as a refrigerant. At a temperature of 20C, the saturated pressure is 57.2 bar. The design of CO2 refrigeration systems depends very much on the application. There are a number of different ways that CO2 can be utilised. A single stage subcritical CO2 system is simple but it also has disadvantages due to the limitation in temperature and high pressure. The transcritical (supercritical) CO2 system is only interesting for small systems, where system pressure is not an important design feature. A number of research programs are running in the automotive industry for airconditioning, but also for residential airconditioning (e.g. Japan).

CO2 in hybrid systems is the most common system design in industrial refrigeration, because the pressure can be limited to a level where the requirements for components like compressors, controls and valves only differ slightly compared to traditionally industrial refrigeration plants. CO2 systems can be designed in different ways e.g. direct expansion systems, pump circulating systems or CO2 in secondary "brine" systems or combinations of these. Some common industrial systems are described on pages 6 and 7.

Fig. 3: Subcritical 10/35 bar

Fig. 4: Supercritical 10/90 bar

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CO2 - Refrigerant for Industrial Refrigeration

CO2 as a refrigerant in industrial systems

Figure. 5 shows a low temperature refrigerating system (40C) using CO2 as a phase change refrigerant in a cascade system with ammonia on the high-pressure side. The CO2 system is a pump circulating system where the liquid CO2 is pumped from the receiver to the evaporator, where it is partly evaporated, before it returns to the receiver. R717 - CO2 cascade system
+30C

The evaporated CO2 is then compressed in a CO2 compressor, and condensed in the CO2NH3 heat exchanger. The heat exchanger acts as an evaporator in the NH3 system.

R717
CO2 -R717
20C 15C

Pressure

R717

Heat exchanger

+30C (12 bar)

20C (1.9 bar)

CO2 compressor
Enthalpy

40C

Pressure

CO2-receiver

CO2
15C (23 bar) 40C (10 bar)

CO2

Enthalpy 40C

CO2 evaporator

Fig. 5: Diagram of R717/CO2 cascade system

Figure. 6 shows the same system as in fig 5, but includes a CO2 hot gas defrosting system. R717 - CO2 cascade system with CO2 hot gas defrosting
+30C

R717
CO2 - R717 Heat exchanger
20C 15C

Pressure

R717

+30C (12 bar)

CO2 compressor

20C (1.9 bar)

Enthalpy

-40C
Pressure

CO2-receiver

CO2 defrost compressor

CO2

+8C 15C (23 bar) 40C (10 bar)

(43 bar)

CO2
+8C Enthalpy 40C

CO2 evaporator

Fig. 6: Diagram of R717/CO2 cascade system with hot gas defrosting

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CO2 - Refrigerant for Industrial Refrigeration

CO2 as a refrigerant in industrial systems (cont.)

Figure. 7 shows a low temperature refrigerating system (40C) using CO2 as a "brine" system with ammonia on the highpressure side. The CO2 system is a pump circulating system, where the liquid CO2 is pumped R717 - CO2 brine system
+30C

from the receiver to the evaporator. Here it is partly evaporated, before it returns to the receiver. The evaporated CO2 is then condensed in the CO2-NH3 heat exchanger. The heat exchanger acts as an evaporator in the NH3 system.

R717
CO2 - R717 Heat exchanger
45C 40C

Pressure

R717

+30C

(12 bar)

45C

(0.5 bar)

Enthalpy

40C
Pressure

CO2-receiver

CO2

40C

(10 bar)

CO2

Enthalpy 40C

CO2 evaporator

Fig. 7: Diagram of R717/CO2 brine system

Design pressure

There are 2 important factors to take into consideration when determining the design pressure. 1. The pressure during stand still. The pressure during stand still can be very high and this has to be taken into consideration:

2. Defrosting pressure by CO2 hot gas defrosting: Depending on the actual design, different ways of defrosting can be applied (natural, water, electrical or CO2 hot gas defrosting). The CO2 hot gas defrosting is the most efficient, especially at low temperatures, but it also has the highest pressure demand. With a design pressure of PS=50 bar, it is possible to reach a defrosting temperature of approx. 9-10C. The saturated pressure at 9C is 43.9 bar-g. By adding 10% for the safety valves and approx. 5% for pressure peaks, the requirement is for pressure PS ~ 50 bar-g. (See figure 8 and 9). There is not one common method to perform defrosting. All methods, as described above, are used, depending on the system, but also on the availability of suitable compressors and other components.

A small separate refrigeration system can be used to keep the liquid temperature at a level, where the saturated pressure is lower than the design pressure Designing the system with an expansion vessel of a size that prevents the pressure from exceeding the design pressure. Designing the plant so that it can withstand the saturated pressure at the design temperature (approx. 80 bar)

From Danfoss' experience, it would appear that the most common solution for industrial refrigeration applications, is to use a small separate refrigeration system to cool down the liquid CO2.

Danfoss A/S (RC-CM / MWA), 12 - 2002

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CO2 - Refrigerant for Industrial Refrigeration

Design pressure (cont.)

60 55 50
Pressure (bar)

CO2

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 (C) 10 20

Fig. 8

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

Saturated pressure

Fig. 9

Efficiency

In CO2-NH3 cascade systems it is necessary to use a heat exchanger. Introducing exchangers creates a loss in the system efficiency, due to the necessity of having a temperature difference between the fluids. In CO2 "brine" systems, and in pump circulating systems with oil free compressors, there is no oil present in the circulated CO2. From an efficiency point of Due to the thermodynamic properties of CO2, in particular the relative high pressure level, the compressor capacity is significantly higher for CO2 than it is for NH3. The pipe

However, compressors running with CO2 have a better efficiency and heat transfer is greater. The overall efficiency of a CO2-NH3 cascade system is not reduced when compared to a traditional NH3 system [3]. view, this is an optimum solution due to good heat transfer coefficients in the evaporators. However, it requires that all valves, controls and other components can operate "dry". dimensions in the vapour lines are smaller, but in liquid lines are larger. (See figure 10 and 11).

Oil in CO2 systems

Component size

[3] Stoecker, Will

IIAR Ammonia Refrigeration Conference Nashville TN 2002

Danfoss A/S (RC-CM / MWA), 12- 2002

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Component size (cont.)

DN

Example: 100 kW, ncirc = 3 DT - 1(K)

Wet suction line

100 80 60 40 20 0

R717

CO2

Wet suction line

Velocity (m/s)
25 20 15 10 5 0

Wet suction line

R717

CO2

Example: Return line CO2 and a NH3 pump circulating system with a capacity of 100 kW, circulating rate of 3, is designed to have a temperature drop from the evaporator to the receiver on 1K. Fig. 10

Wet suction line

0.4

p (bar)

0.3 0.2 0.1 0

R717

CO2

Example: 100 kW, ncirc = 3 Velocity ~ 0,8 (m/s)

Liquid line
35 30 25 20 15 10 5 0

DN

R717

CO2

Liquid line
0.05

Example: Liquid line CO2 and a NH3 pump circulating system with a capacity of 100 kW, circulating rate of 3, is designed to have a velocity on 0.8 m/s. Fig. 11

p (bar)
0

Liquid line

R717

CO2

Refrigerant charge in CO2-NH3 cascade systems

EN 378 classifies CO2 as a L1 non-toxic, non-flammable refrigerant and ammonia as a L2 toxic refrigerant. Even though NH3 has been used for many years, the requirements have become more restricted in recent years, in particular in some European countries. Therefore, there is a great interest in

minimizing the NH3 charge. A CO2-NH3 cascade system is a perfect solution with the NH3 being limited to a small charge, which can be contained in a special machinery room having the necessary safety arrangements.The CO2 is then distributed to all coolers.

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CO2 - Refrigerant for Industrial Refrigeration 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

Material compatibility

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.

Approximation of relative permeation, diffusion and solubility of different gases in polymers [4].
Relative permeation coefficient Q N2 - Nitrogen CO2 Carbon Dioxide CH4 - Methane He - Helium O2 - oxygen 1 24 3.4 15 3.8 Relative diffusion coefficient D 1 1 0.7 60 1.7 Relative solubility coefficient S 1 24 4.9 0.25 2.2 1 24 7 0.004 1.29 S/D

Explanation The permeation "Q" indicates the amount of gas penetrating into the material. The permeation depends on pressure and in particular the temperature. The diffusion "D" indicates the amount of gas passing through the material.

The solubility "S" indicates the amount of gas dissolved (accumulated in) the material. S/D indicates the sensitivity of creating blisters and fractures in polymers. The high value of S/D for CO2 indicates that CO2 is one of the strongest promoters.

Danfoss has carried out a number of tests to ensure that components released for use with CO2 can withstand the impact of CO2 in all aspects. The tests have shown that CO2 is different, and modifications have to be made on some products. The large amount of CO2, which can dissolve in polymers, has to be taken into consideration. Some commonly used Water in CO2 systems In NH3 systems it is well known that there are reaction problems with oil, oxygen, water and solid contaminations, but these are all handled today by frequent oil changes, and use of air purges. Compared to NH3, CO2 is less sensitive, but if water is present, problems may occur.

polymers are not compatable with CO2, and others require different fixing methods e.g. sealing materials. When the pressure is close to the critical pressure and the temperature is high, the impact on polymers is much more extreme. However, those conditions are not important for industrial refrigeration as pressure and temperatures are lower for these systems.

How can water penetrate into a CO2 system? The pressure of CO2 systems is always above the atmospheric pressure; therefore there are no risks that leaks may cause penetration of H2O into the system. 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.

[4] Leisenheimer, Bert and Thomas Fritz , Eaton Corporation. Aeroquip Groupe IIF - IIR Commission B1,B2 and E2, Purdue University

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Water in CO2 systems (cont.)

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]

2000

R134a
1000 800

mg of water/kg refrigerant [ppm]

1200

R134a
1500

CO2

600

1000

400

500

200

0 -60

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

0 -60

-50

-40

-30

-20

-10

10

20

30

40

50

60

Tem perature [ oC]

Fig. 12: Water solubility

mg of water/kg of refrigerant [ppm]

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

CO2 + ICE

CO2 + Water

CO2 Gas Phase

(Y-Axis Linear)

Water solubility in Refrigerants

CO2 + H2O gasPhase

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

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

NH3

R134a R22

1200 1000 800

R404A
600 400 200 0 -60 -50 -40 -30 -20 -10 0 10 20
Temperature [C]

CO2
30 40 50 60

Fig. 13: Water solubility

The acceptable amount of water in CO2 systems is much lower than in systems with other common refrigerants. If the water content exceeds the dew-point, and the temperature is below 0C, the water will freeze, creating a risk of problems with equipment in the system e.g. blocking control valves.

The water can very easily be removed by mounting a drier in the system. Driers in CO2 are very efficient, and are normally mounted in the liquid line to avoid any unnecessary pressure drops being created.

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CO2 - Refrigerant for Industrial Refrigeration

Water in CO2 systems (cont.)

mg of water/kg refrigerant [ppm]
100 90 80 70 60 50 40 30 20 10 0 -50

Water in CO2 Danfoss Sight Glass SGN in CO2

"Wet"

"Dry"

-40

-30

-20 -10 Tem perature [C]

10

20

Fig. 14: SGN moisture indication for CO2

CO2 system with filter drier and indicator

Evaporator

Condenser

Filter drier

Moisture indicator

Fig. 15: CO2 systems with filter drier and indicator

Leaks in CO2-NH3 cascade systems

The most critical leak in a CO2-NH3 cascade system is in the heat exchangers between CO2 and NH3. The pressure of the CO2 will be higher than the NH3, so the leak will occur into the NH3 system, which will become Due to the Thermodynamic properties of CO2, in particular the triple point, which is located at much higher pressure than for all other common refrigerants, the formation of solid CO2 can occur. If a safety valve is mounted in a CO2 system at e.g. 50 bar, the pressure in the downstream (outlet) line from the safety valve will pass the triple point at 5.2 bar. Below the triple point, CO2 will change from a mixture of

contaminated. The solid substance ammonium carbonate is formed immediately when CO2 is in contact with NH3. Ammonium carbonate is corrosive [5].

Safety valves in CO2 systems

liquid and vapour into a mixture of solid and vapour .The formation of solid CO2 in the downstream line can, in the worst case, block this line. The most efficient solution to this problem is to mount the safety valve without an outlet line, thus blowing directly into the atmosphere. The phase change of the CO2 does not take place directly in the valve, but just after the valve, and in this case in the atmosphere

[5] Broesby-Olsen, Finn Laboratory of Physical Chemisty, Danfoss A/S IIF - IIR Commissions B1, B2, E1 and E2 - Aarhus Denmark 1996

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CO2 - Refrigerant for Industrial Refrigeration

Pressure (bar)

Safety valves in CO2 systems (cont.)

CO2
100 73.6

+31C

Supercritical Liquid

Safety valve 50 bar Safety valve 35 bar

Solid - Liquid
10

Liquid - Vapour

Safety valve 35 bar 0% solid CO 2 at the triple point

Solid
5.2 - 56.6C
Safety valve 50 bar 5% solid CO 2 at the triple point

Solid - Vapour
- 78.4C

Vapour
1 -200 -100 0 100 200 300 400 500 Enthalpy (J)

Fig. 16: Flow in downstream lines from safety valves

Safety

As previously mentioned, CO2 is classified as a non-toxic refrigerant, but unlike NH3, CO2 has no distinctive smell. Safety Aspects of CO2 [6] Carbon dioxide replaces air, and causes lack of oxygen. In the presence of sufficient oxygen, CO2 has a narcotic effect at stronger concentrations. With smaller amounts, CO2 has a stimulating effect on the respiratory The symptoms associated with the inhalation of air containing carbon dioxide are, with increasing carbon dioxide concentrations. 0.04% 2% 3% 5% 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 is tolerated by most persons, but it is physically burdening Short term 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 consciousness, and shock(i.e. a sharp drop in blood pressure) The victims recover very quickly in fresh air. 18-20% Symptoms similar to those of a stroke.
Note: The data, valued for adults with good health

centre. Due to the acidic characteristics of CO2, a certain local irritation may appear, particularly on the mucous membrane of the nose, throat and eyes, and it may induce coughing, as well.

8%

Conclusion

The availability of components for CO2 industrial refrigeration systems having reduced pressure to approx. 30 bar is good. Several manufacturers of equipment for the traditional refrigerants can also supply some components for CO2 systems, but the availability of higher-pressure components for CO2 industrial refrigeration systems is limited. An important factor in the speed of
[6] Ahlberg, Kersti

introducing CO2 systems, is very much dependent on the availability of critical components for high pressure CO2. Within the area of industrial refrigeration, CO2 will not replace ammonia. The industrial CO2 systems are all hybrid systems, which also require ammonia on the high temperature side of the system, but only with a small ammonia charge.

AGA Gas Handbook 1985 ISBN 91-970061-1-4

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CO2 - Refrigerant for Industrial Refrigeration

Danfoss valves and controls for CO2

Danfoss industrial refrigeration valves have been used for CO2 systems for more than 15 years. The CO2 systems have been refrigeration, process and fire fighting systems where the pressure has been limited to 25 bar. During the last few years, Danfoss has supplied an increasing number of valves for several CO2 systems at different pressure stages up to 50 bar.

Today, Danfoss is offering a broad programme of industrial products applicable for CO2, however this is dependent on demands regarding the design pressure. The table below includes the components available for the different pressure stages.

High Pressure Components - CO2

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

Pressure (bar)

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 (C) 10 20

Danfoss industrial refrigeration High pressure components

Modulating liquid level regulators Main Valves, Solenoid Valves Pilot Valves for PM Main Valves Motor Regulating Valves Motor Expansion Valves Float Valves Stop Valves Regulating Valves Stop Check Valves Gas Powered Stop Valve Safety Valves and Change Over Valves
PMFL PMFH PM1 PM3 PML PMLX EVM Other pilots MRV MEV HFI SV SVA SVA REG SCA GPLX SFV BSV DSV POV FIA NRVA NRVS CHV EVRA EVRS AKVA AKS 45 all all

DN

PS PS PS 25 40 50 bar bar bar

The product can be used in standard version. All products are CE approved

25-65 25-125

all all 100, 150 1-3 & 4,5,6 15-200 250, 300 all all 80, 100, 125 15, 20, 25 8 32 40, 50, 80 all all 20, 25, 32 all all all all all

25-65 25-65 100 - 150 15-200 250-300 15 - 40 20-125 80-125 15 - 25 8 32 40-80 32-200 15 - 65 20-32 20 - 40 15-40 15-25 15-40

The product must be manufactured in a special version (higher test pressure, marking and documentation). All products are CE approved

**) 1

Filters Check Valves

Solenoid Valves Liquid Injection Level Indicator

**) 1 **) 1 **) 1

**) 1

The product must be manufactured in a special version (design modification, higher test pressure, marking and documentation). All products are CE approved

All marked components are applicable for CO2 in the standard execution. These components are applicable for CO2 40 bar or 50 bar.

In connection with the CE approval of these valves, Danfoss has implemented product modifications and approved them for the maximum pressure. The products are subject to specific testing and marking, but all of them are CE approved.

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CO2 - Refrigerant for Industrial Refrigeration

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CO2 - Refrigerant for Industrial Refrigeration

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