As discussed in Heat pump technology, closed-cycle compression type heat pumps require a working fluid. Traditionally, the most common working fluids for heat pumps have been:
- CFC-12 Low- and medium temperature (max. 80°C);
- CFC-114 High temperature (max. 120°C);
- R-500 Medium temperature (max. 80°C);
- R-502 Low-medium temperature (max. 55°C);
- HCFC-22 Virtually all reversible and low-temperature heat pumps (max. 55°C).
Due to their chlorine content and chemical stability, CFCs (Chlorofluorocarbons) are harmful to the global environment. They have both a high ozone depletion potential (ODP) and a global warming potential (GWP). Environmental effects can also be represented with the Total Equivalent Warming Impact (TEWI) concept to determine the overall contribution of CFC alternatives to global warming. TEWI is the sum of the direct contribution of greenhouse gases used tomake or operate the systems and the indirect contribution of the carbon dioxide emissions resulting from the energy required to run the systems over their normal lifetime.
CFCs belong to the group of prohibited refrigerants. Due to their high ozone depletion potential the manufacture of these refrigerants, and their use in new plants, is now banned although they are still permitted in existing plants. However, only purified (recycled) refrigerants from decommissioned and retrofitted plants are available. It is therefore expected that these refrigerants will become more and more expensive, and at some point will no longer be available. This group includes the following refrigerants: R-11, R-12, R-13, R-113, R-114, R-115, R-500, R-502, R-13B1.
As a general requirement, heat pumps using alternative working fluids should have at least the same reliability and cost effectiveness as (H) CFC systems. Moreover, the energy efficiency of the systems should be maintained or be even higher, in order to make heat pumps an interesting energy-saving alternative. In addition to finding new and environmentally acceptable working fluids, it is also important to modify or redesign the heat pumps. Generally speaking, the energy efficiency of a heat pump system depends more on the heat pump and system design than on the working fluid.
HCFC (hydrochlorofluorocarbons) working fluids also contain chlorine, but they have much lower ODP (ozone depletion potential) than CFCs, typically 2-5% of CFC-12, due to a lower atmospheric chemical stability. The GWP (global warming potential) is typically 20% of that of CFC-12. H-CFCs are so-called transitional refrigerants. They should only be used for retrofit applications. H-CFCs include R-22, R-401, R-402, R-403, R-408 and R-409. Table 1 shows the phase-out schedule of CFCs and HCFCs for industrialised countries, which was agreed under the Montreal Protocol and its amendments and adjustments. HCFCs should be phased out for industrialised countries by the year 2020, and should be phased out entirely by 2040. The European Union has adopted an accelerated phase-out schedule for these substances, which requires them to be phased out by January 2015. Some countries in Europe (Sweden, Germany, Denmark, Switzerland and Austria) also have an accelerated schedule and will phase out R-22 for new systems between 1998 and 2002.
|1 January 1996
||CFCs phased out (1) |
HCFCs frozen at 1989 levels of HCFC + 2.8% of 1989 consumption of CFCs (base level)
|1 January 2004
||HCFCs reduced by 35% below base levels |
|1 January 2010
||HCFCs reduced by 65% |
|1 January 2015
||HCFCs reduced by 90% |
|1 January 2020
||HCFCs phased out allowing for a service tail of up to 0.5% until 2030 for existing refrigeration and air-conditioning equipment |
HFCs (hydrofluorocarbons) can be considered long-term alternative refrigerants. This means that they are chlorine-free refrigerants such as R-134a, R-152a, R-32, R-125and R-507. Since they do not contribute to ozone depletion, these are long-term alternatives to R-12, R-22 and R-502. However, they do still contribute to global warming. Special attention must be given to the use of lubricants. Mineral oils are non-miscible with these refrigerants. Normally only ester-based lubricant oils recommended by the refrigerant manufacturer should be used. Mineral oil residues must be completely removed during retrofitting.
- HFC-134a is quite similar to CFC-12 in thermophysical properties. The coefficient of performance (COP) of a heat pump with HFC-134a will be practically the same as for CFC-12. At low evaporating temperatures (below -1°C) and/or high temperature lifts the COP will be slightly lower.
- HFC-152a has mainly been used as a part of R-500, but it has also been successfully applied in a number of small heat pump systems and domestic refrigerators. HFC-152a is currently applied as a component in blends. Because of its flammability, it should only be used as a pure working fluid in small systems with low working fluid charge (see also Hydrocarbons).
- HFC-32 is moderately flammable and has a GWP close to zero. It is considered as a suitable long-term replacement for HCFC-22 in space-conditioning, heat pump and industrial refrigeration applications. Due to its flammability, HFC-32 is usually applied as a main component in non-flammable mixtures replacing R-502 and HCFC-22.
- HFC-125 and HFC-143a have properties fairly similar to R-502 and HCFC-22. They are mainly applied as components in ternary mixtures replacing R-502 and HCFC-22. The GWPs are, however, about three times as high as that of HFC-134a.
Blends or mixtures represent an important possibility for replacement of CFCs, both for retrofit and new applications. A blend consists of two or more pure working fluids, and can be zeotropic, azeotropic or near-azeotropic. Azeotropic mixtures evaporate and condense at a constant temperature, the others over a certain temperature range (temperature glide). The temperature glide can be utilised to enhance performance, but this requires equipment modification. The advantage of blends is that they can be custom-made to fit particular needs.
Early blends for replacement of CFC-12 and R-502 all contained HCFC-22 and/or other HCFC working fluids, such as HCFC-124 and HCFC-142b, and are therefore considered as transitional or medium-term working fluids.
The new generation of blends for replacement of R-502 and HCFC-22 are chlorine-free, and will mainly be made from HFCs (HFC-32, HFC-125, HFC-134a, HFC143a) and hydrocarbons (e.g. propane). Two of the most promising alternative working fluids for eventually replacing R-22 in heat pumping applications are the blends R-410A and R407-C, that are discussed below in more detail. The main difference between the two is the chemical composition: R-410A is a mixture of R-32 and R-125 with minimal temperature glide, while R-407C consists of R-32, R-125 and R-134A and has a large temperature glide. Annex 18 of the IEA Heat Pump Programme has performed a detailed study on thermophysical properties of blends.
- R-407C is the only refrigerant available for immediate use in existing R-22 plants Ð thermal properties and operating conditions are close to those of R-22. However, because of its temperature glide it is only suitable for certain systems. The use of this refrigerant is increasing, although there are still some engineering difficulties for service companies and manufacturers.
- Research has shown that the use of R-410A can result in an improved COP compared to R-22. Using R-410A means that overall cost reductions can be achieved, because the system components, particularly the compressor, can be significantly downsized since it has a higher volumetric capacity. The main disadvantage is the higher operating pressure compared to R-22, which indicates that the pressure-proof design of most components should be reviewed. R-410A is very popular, mainly in the US and Japan, for packaged heat pumps and air-conditioning units. Commercial R-410A components for small- and medium-sized refrigeration systems are either already available or under development.
Natural working fluids
Natural working fluids are substances, naturally existing in the biosphere. They generally have negligible global environmental drawbacks (zero or near-zero ODP and GWP). They are therefore long-term alternatives to the CFCs. Examples of natural working fluids are ammonia (NH3), hydrocarbons (e.g. propane), carbon dioxide (CO2), air and water. Some of the natural working fluids are flammable or toxic. The safety implications of using such fluids may require specific system design and suitable operating and maintenance routines. For more information on Natural working fluids, see Annex 22.
- Ammonia (NH3) is in many countries the leading working fluid in medium- and large refrigeration and cold storage plants. Codes, regulations and legislation have been developed mainly to deal with the toxic and to some extent, the flammable characteristics of ammonia. Thermodynamically and economically ammonia is an excellent alternative to CFCs and HCFC-22 in new heat pump equipment. It has so far only been used in large heat pump systems, and high-pressure compressors have raised the maximum achievable condensing temperature from 58°C to 78°C.
Ammonia can also be considered in small systems, the largest part of the heat pump market. In small systems the safety aspects can be handled by using equipment with low working fluid charge and measures such as indirect distribution systems (brine systems), gas-tight rooms or casing, and fail-safe ventilation. Copper is not compatible with ammonia, so that all components must be made of steel. Ammonia is not yet used in high-temperature industrial heat pumps because there are currently no suitable high-pressure compressors available (40 bar maximum). If efficient high-pressure compressors are developed, ammonia will be an excellent high-temperature working fluid.
- Hydrocarbons (HCs) are well known flammable working fluids with favourable thermodynamic properties and material compatibility. Presently, propane, propylene and blends of propane, butane, iso-butane and ethane are regarded as the most promising hydrocarbon working fluids in heat pumping systems. HCs are widely used in the petroleum industry, sporadically applied in transport refrigeration, domestic refrigerators/freezers and residential heat pumps (notably in Europe). Due to the high flammability, hydrocarbons should only be retrofitted and applied in systems with low working fluid charge. To ensure necessary safety during operation and service, precautions should be taken such as proper placing and/or enclosure of the heat pump, fail-safe ventilation systems, addition of tracer gas to the working fluid, use of gas detectors etc.
- Water is an excellent working fluid for high-temperature industrial heat pumps due to its favourable thermodynamic properties and the fact that it is neither flammable nor toxic. Water has mainly been used as a working fluid in open and semi-open MVR systems, but there are also a few closed-cycle compression heat pumps with water as working fluid. Typical operating temperatures are in the range from 80°C to 150°C. 300°C has been achieved in a test plant in Japan, and there is a growing interest in utilising water as a working fluid, especially for high- temperature applications. The major disadvantage with water as a working fluid is that the low volumetric heat capacity (kJ/m3) of water. This requires large and expensive compressors, especially at low temperatures.
- CO2 is a potentially strong refrigerant that is attracting growing attention from all over the world. CO2 is non-toxic, non-flammable and is compatible to normal lubricants and common construction materials. The volumetric refrigeration capacity is high and the pressure ratio is greatly reduced. However, the theoretical COP of a conventional heat pumping cycle with CO2 is rather poor, and effective application of this fluid depends on the development of suitable methods to achieve a competitively low power consumption during operation near and above the critical point. CO2 products are still under development, and research continues to improve systems and components. A prototype heat pump water heater has already been developed in Norway. CO2 is now being used as a secondary refrigerant in cascade systems for commercial refrigeration.