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Paper synthetic refrigerants

Comparison of modern synthetic refrigerants for merchant ships
Synopsis
Due to environmental damage caused by old CFC refrigerants like R12 and R502 and the HCFC refrigerants like R22, there is currently a worldwide search to find the best, safest and most environmentally friendly alternative. At present, the most commonly applied alternatives are the chlorine-free HFC refrigerants R134a, R404A, R407C, R410 and R507. However, their thermodynamic behaviour is very dependent upon the evaporation temperature. Besides interest in synthetic refrigerants, more and more attention is being given to natural refrigerants such as carbon dioxide (CO2) and ammonia (NH3 ), hydrocarbon refrigerants such as propane and ISO-butane and even water and air. This report discusses the differences between the various modern synthetic HFC refrigerants. In addition, it also provides some possible scenarios that involve natural refrigerants and methods of refrigeration that do not involve compression and expansion of a refrigerant gas. The data presented in this report is based upon the following background unless stated otherwise Since 1992, politicians the world over have been involved in reducing the environmental damage caused by refrigerants. During recent years, depletion of the ozone layer has occurred due to chlorine in CFC and HCFC refrigerants. In 1992, at the first Montreal Protocol meeting in Copenhagen, the first phasing out plan for Europe was developed to ban the use of CFC and HCFC. This was a long-term plan to enable the refrigeration industry to find an acceptable replacement for the old refrigerants. Recently, research within the refrigeration industry has come up with acceptable alternatives. Therefore, the time scale of the phase-out plan was shortened in many countries, and restrictions in the use of HCFCs were tightened. Other fields and other components such as the use of screw compressors instead of piston compressors, for example may show different results. Specific applications are provision plants, condensing units for air conditioning, chiller units and inert gas systems for oil and gas tankers.

Worldwide regulations the Montreal Protocol

dedicated YORK Refrigeration Marine products for marine application YORK piston compressors type SBO, CMO and SMC 10 K superheating suction gas 2 K liquid subcooling efficiency of electro-motors is 8085% evaporation temperatures between approximately -30C and +8C condensation temperatures between 35C and 48C piston compressors and water-cooled condensers.

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Table 1: Montreal Protocol phasing out programme for (H)CFC (R22)

HCFC phasing out programme Montreal Protocol versus EU Decree

Montreal Protocol result of the 7th meeting in Vienna, December 1995 Year 1996 Amount of production allowed Reference: 2.8% of 1989 CFC use + 1989 HCFC use, ODP weighted Production EU Decree No. 2037/2000

Use/Import/own production

Ban on use in following applications

1997 1999

Reference year Reference: 2.8% of 1989 CFC use + 1989 HCFC use, ODP weighted Freeze according to reference year Reference: 2.0% of 1989 CFC use + 1989 HCFC use, ODP weighted Reduction to 85% Public cold stores & warehouses + plants with shaft power > 150 kW All stationary refrigeration and air conditioning systems July 1: Air conditioning systems with capacity < 100 kW Reversible air conditioning and heat pump systems Service of existing systems with new HCFC Service of existing systems with recycled HCFC Reduction to 15% END OF PRODUCTION

2000

2001

2002

2003 2004 2008 2010 2014 2015 2020 2025 2030

Reduction to 65% Reduction to 35% Reduction to 35% Reduction to 20% Reduction to 10% Reduction to 0.5% END OF PRODUCTION

Reduction to 45% Reduction to 30% Reduction to 25% END OF IMPORT & PRODUCTION

At the latest Montreal Protocol meeting in Beijing in December 1999, the decisions and time-scales made in the previous meeting in Vienna in 1995 were once again emphasised. The Montreal Protocol differentiates between so-called article 5 nations and non-article 5 nations. An article 5 nation is a developing country whose annual consumption of controlled substances per capita does not exceed 0.3 kg (see table 3). The phase-out deadlines for article 5 nations are a little bit later than for non-article 5 nations. At the moment, a total of about 175 nations have subscribed to the Montreal Protocol. In marine refrigeration installations, the controlled substances CFC and HCFC are widely used. In non-article 5 nations, CFCs such as R12 have not been produced since 1996. The same will happen with HCFC refrigerants like R22 by 2030 or even earlier. These refrigerants will be replaced by so-called HFC (chlorine-free) refrigerants.
Controlled substance Current phase-out deadlines % eliminated Nonarticle 5 Article 5 (developing countries) 1 Jan 2010 1 Jan 2010 1 Jan 2010 1 Jan 2040
Not established Freeze in 2001

Table 2: Montreal Protocol phase-out deadlines

CFCs Halons Carbon Tetrachloride HCFCs HBFCs Methyl Bromide Methyl Chloroform

100 100 100 100 100 100 100

1 Jan 1996 1 Jan 1994 1 Jan 1996 1 1 1 1 Jan Jan Jan Jan 2030 1996 2010 1996

2015

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Modern synthetic refrigerants

Synthetic refrigerants are defined as all refrigerants that do not exist in nature. The important synthetic refrigerants for the refrigeration industry are the so-called CFC, HCFC and HFC gases. CFCs are refrigeration gases whose molecules consist of at least one carbon and two chlorine atoms, e.g. R12 and R502.

HCFCs are refrigeration gases whose molecules consist of at least one carbon and one chlorine atom, e.g. R22. HFCs are refrigeration gases whose molecules consist of at least one carbon atom and no chlorine atoms. These relatively new refrigeration gases are the modern refrigerants, or R22 replacement refrigerants. The most popular are R404A, R407C, R134a, R410 and R507.

Table 3: Temperature glides, ODP, GWP and TEWI values for some modern refrigerants

Name

Components [mass%]

Practical temp. glide at ET = -25C

Practical temp. glide at ET = +5C

Practical temp. glide at CT = 42C O.D.P. G.W.P. T.E.W.I.*

R22 R404A R407C R134a R410A R507

R22 [100] R125 [44], R143A [52], R134a [4] R32 [23], R125 [25], R134a [52] R134a [100] R32 [50], R125 [50] R125 [50], R143A [50]

0.0 K < 0.5 K (not noticeable) ~5K 0.0 K < 0.05 K (not noticeable) < 0.05 K (not noticeable)

0.0 K < 0.5 K (not noticeable) ~5K 0.0 K < 0.2 K (not noticeable) < 0.05 K (not noticeable)

0.0 K < 0.2 K (not noticeable) ~5K 0.0 K < 0.05 K (not noticeable) < 0.05 K (not noticeable)

0.05 0.00 0.00 0.00 0.00 0.00

1500 3260 1525 1300 1725 3300

1.00 ~1.13 ~ 1.14 ~ 1.19 ~ 1.13 ~ 1.12

O.D.P. Ozone Depletion Potential relative reactivity value with Ozone (O3), reference 1.0 for R11* G.W.P. Global Warming Potential reference 1.0 for CO2 , IHT of 100 years* T.E.W.I. Total Equivalent Warming Impact summation of the direct impact of GWP and the indirect impact through energy consumption of the installation, reference 1.0 for R22* Temperature glide is the temperature difference between the beginning and the end of the evaporation/condensing process. *Values are based upon refrigerant leakage of 3% per year, an installation lifetime of 15 years, an average CO2 emission of 0.6 [kg/kWe h] and a recycle factor for the refrigerant of 95%. **The listed GWP values are from IPCC's report "Climate Change 1995" (IPCC = Intergovernmental Panel on Climate Change). Some of the values have changed since, but national greenhouse gas emission accounting and the Kyoto Protocol targets are based on the listed values.

Comparison of discharge temperatures of modern refrigerants in compressors

120 Absolute temperature [C]

100

80

60 R22 40 Discharge temperature at ET= -25C and CT= 42C Discharge temperature at ET= +5C and CT= 42C R404A R507 R407C R134a R410 R22 R404A R507 R407C R134a R410

Figure 1: Practical discharge temperatures of some modern refrigerants in compressors

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Pressures and temperatures

Designing a refrigeration installation means that a range of components must be selected and put together. Refrigeration technology has been developed for over a century and is usually applied within pressure ranges of up to 25 bar (gauge) and temperatures between minimum ET 40C and maximum CT +140C for simple refrigeration installations. The behaviour of comparable modern refrigerants depends mainly on the evaporation temperature. Figures 1 and 2 show temperatures and pressures resulting from typical provision room plant design conditions ET -25C/CT 42C and typical air conditioning plant conditions ET +5C/CT 42C. No difficulties are expected with the modern refrigerants regarding the different temperatures that occur because all temperatures are comparable or even lower than the temperatures for R22.

But when the different pressures and temperatures are considered at -25C , the refrigerants R134a and R407C operate at quite a low pressure. This means that the density of the refrigeration gas on the suction side of the compressor is relatively low (very few molecules per m3), which results in poor volumetric performance and a risk of drawing air which implies moisture into the system if leaks occur. It can be concluded that the R134a and R407C refrigerants are not very suitable for low temperatures. For R410, the discharge pressure can exceed the normal plant design pressure of 25 bar (gauge). This implies that non-standard components must be used, especially when the condensation temperature can be above 42C.

Comparison of pressures of modern refrigerants

30

25

Absolute pressure [Bara]

20

15

10

R22

R404A

R507

R407C R134a

R410

R22

R404A

R507

R407C R134a

R410

R22

R404A

R507

R407C R134a

R410

Suction pressure at ET= -25C

Suction pressure at ET= +5C

Discharge pressure at CT= 42C

Figure 2: Practical pressures of some modern refrigerants

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Energy consumption and installation costs

Every refrigeration installation consumes energy. Many factors influence energy consumption, and one of these is the refrigerant used. When comparing energy consumption for modern refrigerants, no new refrigerant performs better than R22. The three refrigerants that perform best hereafter in terms of energy consumption are R404A, R507 and R410.

The relative refrigerant flow shown in figures 3a and 3b defines the compressor size. Adjusting the rpm between 1000 and 1800 can vary the compressor capacity. Relatively large compressors are limited to 1500 rpm. For refrigerants R404A, R407C and R507, the necessary refrigerant swept volume can, in most cases, be achieved with the same type of compressor as used for R22, just by adjusting the rpm of the compressor.

Comparison of the volume flow and C.O.P. of modern refrigerants at ET= -25C/CT = +42C

100%

Relative figures, R22 based

80% 60% 40% 20% 0% -20% -40% R404A R507 R407C R134a R410 R404A R507 R407C C.O.P. R134a R410

Swept volume

Comparison of the volume flow and C.O.P. of modern refrigerants at ET= +5C/CT = +42C

80%

Relative figures, R22 based

60% 40% 20% 0% -20% -40% R404A R507 R407C R134a R410 R404A R507 R407C C.O.P. R134a R410

Swept volume

Figure 3a + 3b: Relative swept volume and C.O.P. values of some modern refrigerants

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To achieve the same capacity with R134a, a much bigger compressor should be selected, which involves a greater investment. For R410, a compressor that is about 30% smaller must be selected. In addition to operating costs, the initial installation costs are an important consideration. Except for R410, these costs are more or less defined by the size of the main components, such as the compressor, condenser and evaporator. Because of the high discharge pressures associated with R410, at this moment special components are required. Because of recent developments it is expected that in near future no special components need to be used anymore. Although YORK Refrigeration has no preference for a specific refrigerant, the popularity of R404A can be explained by looking at the figures. Indications are for an increase in the use of R410 in the near future.

Availability and the changing price of synthetic refrigerants

All modern HFC refrigerants are available throughout the world. New refrigerants are not expected to be added to the list in the near future. When looking at the demand for refrigerants in the marine market, the popularity of R404A is rising, while the popularity of R134a is decreasing and the popularity of R407C and R507 is expected to remain stable at relatively low levels over the next few years, but will eventually decrease.

Comparison of modern refrigerants - Main component costs

Relative cost, R22 based Compressor Compressor Compressor Compressor Compressor 80% Evaporator Condenser 60% 40% 20% 0% Evaporator Evaporator Evaporator Evaporator Condenser Condenser Condenser Condenser

R404A

R407C

R507

-40%

Figure 4: Main component costs (the price for R410 in the future)

Comparison of modern refrigerants - Total installation costs

25% 20% Relative cost, R22 based 15% 10% 5% 0% -5% -10%

R404A

R507

R407C

R134a

R410

Figure 5: Total installation costs (value for R410 for future)

R410

-20%

R134a

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The refrigeration industry is very interested in R410, but is concerned about high pressures. In addition, standard components are not yet available on a large scale.

ties as the original refrigerant. However, some electronic expansion valves may have difficulties adjusting correctly. Mixture change of R407C in systems with flooded evapora-

When looking at the present price level of refrigerants, R134a is approximately twice as expensive as R22. R404A and R407C are approximately three times more expensive than R22 and the price levels of R410 and R507 are even higher. The rising popularity of R404A together with the increasing tax charges for R22 will possibly result in some price levelling between these two refrigerants. The diminishing popularity of R407C and R507 may result in higher prices and diminished worldwide availability. Because R134a is common in small household refrigerators, it is unlikely that its price will change significantly. With the development of high-pressure refrigeration components, the popularity of R410 is likely to rise very fast. At this moment, both YORK Refrigeration Marines screw compressors and its piston compressors of up to 8 cylinders are all capable of operating with R410.

tors can occur, but within limits. The gas that is sucked out of the flooded evaporator might have a different mixture than the fluid left over, but this will not exceed a certain level because of the equilibrium between the gas phase and the liquid phase.

Natural refrigerants
Few natural gases are good refrigerants, but most of them have the disadvantage of being toxic and/or inflammable. Ammonia NH3 (R717) has a proven record as an excellent refrigerant in industry for many years. Besides its wide use, it is available throughout the world and is considerably cheaper than synthetic refrigerants. It is also environmentally friendly. The disadvantages of ammonia are that it is toxic and inflammable. Despite these disadvantages, ammonia has had a good safety record and can be safely applied providing appropriate design, installation, maintenance and han-

Mixture change of refrigerant blends

Mixture change of refrigerant blends due to leakage is possible under very special circumstances. These are

dling procedures. The advantages of ammonia as a refrigerant outnumber the disadvantages. Therefore it is expected that the use of ammonia will increase in the future. Hydrocarbons like propane (R290), ethane (R170) and Iso-butane (R600a) can be used as refrigerants in normal systems as well as in extreme low and high-temperature systems. Propane would be an excellent refrigerant in the same temperature range as R22, and provides a comparable efficiency. However, hydrocarbons have the major disadvantage of being explosive and they do not have a proven safety record.

the refrigerant must have a certain temperature glide (so we are only involving R407C) there must be two phases (liquid and gas phases) of the refrigerant present in a certain volume the refrigerant must be at rest (not moved or shaken ) for a relatively long period of at least two days a very small amount of leakage must occur to keep the
remaining refrigerant at rest. Under these circumstances, a certain change of refrigerant mix could occur, which would be left over in the refrigeration installation. Because of the balance between the phases, there is a limit to the amount of mixture change that can take place. In practice, after refilling the installation the refrigerant in the system has more or less the same proper-

Carbon dioxide has a very good heat transfer coefficient, which allows a reduction in heat exchanger size. It also has a very high capacity per displaced volume: between 8 and 9 times the capacity of that of ammonia. The popularity of carbon dioxide can be expected to rise when used as a low

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temperature fluid in cascade systems on e.g. freezing systems on fishing vessels, but it is not likely to be used as a primary refrigerant because of its extremely high working pressures. Nowadays, even water has been used as a direct refrigerant. A demonstration project was built by YORK Refrigeration at the Lego plant in western Denmark and the plant runs successfully. For air conditioning in aircraft (direct air conditioning), the Brayton cycle is commonly used with air as the refrigerant. Recently, the TNO research organisation based in the Netherlands started a study called the air cycle programme in which air is used as the refrigerant. During this research project, a demonstration installation was built for low temperatures. Although the system was very noisy, the results were good. Besides compression cooling systems, the technology involved in absorption cooling systems has been proven for many years. Nowadays a variety of salts are available that achieve an evaporating temperature down till 60C. In absorption refrigeration installations, heat in the form of e.g. steam is the driving force behind the process.

Possible scenarios
The first scenario predicts that the usage of ammonia and CO2 will increase wherever local codes and regulations allow. Innovations in ammonia system design will reduce the refrigerant content of installations thus getting the systems to run below the limits set for charges of refrigerant and minimising the costs of complying with the rules. This trend could accelerate in the short term, and involves non-thermo siphon oil cooling, ammonia plate heat exchangers and secondary systems in order to keep the application of ammonia inside the engine room. R22 will be used where it is allowed and where ammonia is not accepted. In most countries, it is expected that R22 will be abandoned as soon as possible. Therefore, many customers are reluctant to install new R22 systems because other viable alternatives exist. Besides this, it is no longer allowed to use R22 within the EU. The use of modern refrigerants will increase and the use of R22 will decrease. For the marine industry, this primarily means that the application of R404A is taking over from R22. In the near future, the use of natural fluids like carbon diox-

When waste heat can be utilised, these systems become cheap to run, and this technology could prove to be very interesting. However, when a boiler system is required, the issue of operation costs through energy consumption is an additional concern.

ide, air and water in the comfort marine industry will not be of any importance whatsoever neither is it expected that hydrocarbons will prove any competition for the modern refrigerants.

YORK Marine, Cargo Jens Juuls Vej 28 8260 Viby J Denmark Phone +45 87 36 35 00 Fax +45 87 36 35 01 www.yorkref.com marine@yorkref.com

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