Information on refrigerants, as of June 2022

Honest Engineering with the Refolution inside

Thermal energy only flows from warm to cold. Thus, a so-called heat sink is required to process to cool. The heat sink is generated by a chiller. For this purpose, both energy and requires a refrigerant.

Impact and challenge of refrigeration

Many of the refrigerants used (fluorinated refrigerants) are environmentally harmful and internationally regulated (Montreal Protocol or EU F-GaseV). This information sheet summarizes the most important points regarding the selection and availability of refrigerants and gives recommendations. In Germany, around 14% of all electrical energy is used for cooling processes. The resulting emissions have a significant impact on our climate and are referred to as indirect CO2 emissions. Direct emissions from chillers are caused by leaks and the resulting escaping of refrigerants. Refrigerant is also released during maintenance, filling and disposal of the system. Refrigerants have different effects on the environment.

Ozone layer and global warming potential

The first generation of chemical refrigerants (CFC - chlorofluorocarbons) led to the destruction of the ozone layer (ODP - Ozone Depletion Potential), while the subsequent replacement refrigerants (HFC - hydrofluorocarbons and HFC - fully halogenated hydrocarbons) have a high global warming potential (GWP - Global Warming Potential). .

Impact and challenge of refrigeration

The GWP value of a refrigerant defines its global warming potential in relation to CO2 (also known as the CO2 equivalent). CO2 has a normalized GWP of 1. This means that the GWP value indicates by how much the refrigerant has a greater impact on the greenhouse effect than CO2. A GWP value is always related to a time horizon and thus describes the effects on global warming in the given period. For currently applicable regulations, e.g. in Europe, the F-gas regulation is referenced to a GWP100 and therefore describes the effects of a greenhouse gas over a time horizon of 100 years. The latest publication by the IPCC shows that the next 10-20 years will decide whether the international climate agreement will be complied with or not. A consideration of the GWP20 is therefore relevant in terms of climate policy, but not legally binding. As mentioned, the GWP100 applies here.

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  • The most commonly used refrigerants and their GWP20 / GWP100:

    Newly introduced low-GWP refrigerants (HFO – hydrofluoroolefin) have a short atmospheric lifetime and lead to persistent decomposition products (PFAS/T FA) in the atmosphere. This means that the environment is polluted in the long term and more locally and that there is a potential health hazard (e.g. liver damage) for humans and the environment. Current water treatment processes cannot remove these substances. Energy-intensive processes (e.g. reverse osmosis) are required for processing.

    Table 1 shows the most commonly used refrigerants, their GWP and their atmospheric lifetime.

With regard to environmental regulations, many refrigeration systems will no longer meet the legal requirements in the coming years.

F-Gas regulation – reduction of the GWP value

The EU F-Gas Regulation (Regulation (EU) No. 517/2014), which came into force in 2015, aims to reduce CO2 equivalents from fluorinated greenhouse gases to around 21% by 2030. To this end, the total amount of CO2 equivalents, the fluorinated greenhouse gases, permitted on the market is gradually being reduced (see Figure 1). The baseline is 183.1 million tonnes (100%) [3] , which is the average amount of CO2 equivalents placed on the European market between 2009 and 2012. To compensate for this value, the whole of Germany would have to do without road traffic for 1.25 years or stop the agricultural sector for 2.7 years (as of 2020). Refrigeration systems with a charge of >40 tons of CO2 equivalents, which are operated with a refrigerant with a GWP of over 2500, have been prohibited by Article 13 since January 1st, 2020. The exception to this is for systems with a useful temperature below -50 °C and for maintenance and repairs with recycled refrigerants. From 2030, no recycled refrigerants may be used for systems with application temperatures >-50 °C. A revision of the F-Gas Regulation was eventually proposed in 2022.

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  • Proposed changes:

    One of the proposed changes is to increase emission reduction targets for the period 2021-2030.

    The CO2 equivalents are now to be reduced to 5% by 2030 instead of 21%. These tightenings should come into force in the next few years.

F-Gas Regulation - Price Development

Supply and demand determine the price in the free market economy. Regulations and the associated limited availability of refrigerants on the market inevitably lead to a price increase for GWP refrigerants. The first restriction of the maximum amount of CO2 equivalents to be placed on the market in 2017 resulted in a sharp increase in the price of refrigerants. The high rise in the price of refrigerants has led to an illegal market for GWP refrigerants forming within the EU since 2018. As a result of this and the additional storage of refrigerants, according to the Öko-Recherche Report, there was an oversupply of refrigerants in the third quarter of 2019, which led to a price reduction for refrigerants (Figure 2).

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  • F-Gas Regulation - Price Development

    In the latest report from Öko-Research, a price increase of the high GWP refrigerants R134a, R404A, and R410A (average price increases of 24%, 17%, and 15%, compared to Q1/2021) and blends of HFCs and HFOs (R448A , R452A and R449A by 13%, 5%, and 4%). [Source: Monitoring of refrigerant prices against the background of Regulation (EU) No 517/2014 Q1/2022].

Illegal trade complicates the goal of complying with the F-Gas regulation. Achieving the goals requires an accelerated switch to natural refrigerants and the ending of illegal trade.

Task Force to Stop Illegal Imports

A task force was established in the United States in 2021 to prevent any attempt to illegally import or manufacture F-Gases [5].

The task force announced a few months ago (March 2022) that it had prevented illicit shipments of HFCs amounting to approximately 530,000 tonnes of CO2 emissions in the previous ten weeks. This roughly corresponds to the CO2 emissions of 100,000 households in one year. The previous regulations in the EU could not prevent illegal trading with F-gases. In order to make the illegal trade in refrigerants controllable, the customs authorities of the EU countries must be equipped with the right tools.

New Generations of Chemical Refrigerants (HFO) HFO (Fluoroolefin Hydrogen) are 4th generation refrigerants.

New Generations of Chemical Refrigerants (HFO)

Compared to HFCs (hydrofluorocarbons), HFOs have a low GWP and are viewed by the industry as an alternative. The replacement of the climate-damaging refrigerant R-134a (GWP-1430), used for air conditioning in cars, with HFO-1234yf (GWP < 3) is underway. HFO-1234yf has a short atmospheric lifetime of 10-12 days and decomposes 100% to trifluoroacetic acid. Compared to R134a, which has an atmospheric lifetime of 14 years and a 7 to 20% decay to TFA, the switch results in higher and more localized TFA emissions. TFA belongs to the group of short-chain perfluorocarboxylic acids (scPFCAs), which are persistent in the environment and highly mobile in the water cycle. Topic HFO/TFA can be found in our HFO/TFA Report 7.

Today's drinking water treatment plants are unable to filter out TFA, leaving humans directly exposed to enriched TFA in drinking water. The current measurements of TFA in drinking water are below the drinking water guide value for TFA. However, an up to 13-fold increase in concentrations compared to 2000 has already been observed in Switzerland.

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  • Potential liver damage

    In a study (Umwelt Bundesamt, 2020), an increase in ALT (alanine aminotransferase) concentration was observed with increasing TFA concentration. Elevated levels of ALT are a sign of liver damage because destroyed liver cells release these enzymes. Similar symptoms occur with the administration of halogenated inhalation anesthetics, such as the administration of halothane.

The health risks, especially exposure to small amounts of TFA over long periods of time, have not yet been fully researched.

TFA is formed in the body through the oxidation of halothane and an increase in the ALT concentration is recorded after administration and decreases again after administration is stopped. The same characteristic can be seen in the direct addition of TFA to drinking water from the UBA study. Before chemicals are introduced into the environment, it must be proven that they are harmless to both humans and the environment. It is only a matter of time before there will be negative effects on humans and the environment.

ECHA stands for European Chemicals Agency and is based in Helsinki, Finland. ECHA is responsible for the implementation of the EU chemicals regulation REACH, the Regulation concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals, more information can be found here.

Based on the proposal to restrict PFAS (per- and polyfluorinated alkyl substances), submitted to ECHA by the authorities in Denmark, Germany, the Netherlands, Norway and Sweden on 13 January 2023, a ban on several thousand substances is on the cards. The proposal aims to reduce PFAS emissions into the environment and make products and processes safer for people and the environment. A ban would affect various refrigerants, including all HFO refrigerants and some established refrigerants that are also part of refrigerant blends. HFO refrigerants in particular decompose in the atmosphere to form TFA; a highly mobile and persistent short-chain PFAS.

An online information session will be organised on 5 April 2023 to explain the restriction process and to help those who wish to participate in the 6-month consultation phase starting on 22 March 2023.
Furthermore, all low GWP mixtures are affected as they contain HFO.
E.G. R-452A/B, R-454A/B, R-455A, R-469A,

energy efficiency

The aim of energy efficiency measures is to reduce the overall energy requirements of processes by lowering the quantitative and qualitative losses that occur when converting, transporting or storing energy. Cooling systems require more drive energy (with a constant heat sink and a constant cooling capacity) the lower the useful temperatures are. The ratio of the refrigeration capacity and the drive power is described as the refrigeration coefficient of performance. In typical refrigeration systems for air conditioning, the coefficient of performance is in the order of 3. This means that for 1 kW of drive power, a refrigeration system provides 3 kW of refrigeration capacity for air conditioning. The maximum coefficient of performance that can be achieved in a loss-free, reversible process is described by the coefficient of performance of a Carnot cycle. This is purely dependent on the ambient temperature (heat sink) and the useful temperature (heat source). The lower the usable temperature is required, the lower the cooling performance number of a refrigeration machine. Different refrigeration processes have different efficiencies depending on the temperature. Compression refrigeration systems (2-stage booster systems or cascades) are more efficient compared to cold air refrigeration technology down to useful temperatures of -50 °C. From temperatures of -70 °C, cold air cooling technology is most efficient. Liquid nitrogen is often used for process cooling. This process differs fundamentally in that the refrigerant (nitrogen) is consumed and has already been produced in an air separation plant at temperatures of -196 °C. Generating liquid nitrogen at -196 °C requires significantly more energy than generating process temperatures of -80 °C with a refrigeration system. The use of nitrogen at high temperatures therefore leads to high nitrogen consumption and high energy costs, which are usually not included in the balance sheet of the manufacturing company. The choice of refrigeration technology therefore requires knowledge of the sensible areas of application for the different refrigeration technologies. You can find out more about energy efficiency in our freely available ULT report.

Natural refrigerants can replace the high GWP refrigerants currently used on the market!

Natural refrigerants have grown in popularity over the last few decades and technological developments are progressing very well. They are competitive and even more efficient than chemical refrigerants.

Refrigerants currently in use

For example, CO2 heat pumps (GWP = 1) are used for home water treatment or as booster systems for commercial refrigeration. Furthermore, propane (GWP = 3) is used for chillers. Ammonia (GWP = 0) is a refrigerant with good thermodynamic properties and is used in industry due to its high efficiency. Refrigerants such as R404A (GWP3922), R410A (GWP2088) or R507A (GWP3985) are currently used to generate low temperatures (e.g. freeze drying). The global warming potential (GWP) of these refrigerants is regulated by the F-Gas Regulation, which means that the refrigerants will be banned in the future or their use will be so severely restricted that they are only offered at very high prices.

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  • avoid problems

    In order not to be affected by these problems, it is worth switching to natural, environmentally friendly and safe technologies at an early stage. Cooling with air as a natural refrigerant has established itself in various areas over the past few years, including freeze drying, and is considered a forward-looking technology for a fail-safe, efficient and environmentally friendly process. Natural refrigerants are cost-effective, available in unlimited quantities and can already cover almost all refrigeration applications today. With a very low GWP and high energy efficiency, the use of natural refrigerants is therefore recommended.

importance for operators

Due to the refrigerants used (e.g. R404A, R410A, R499A, R23), the majority of refrigeration systems for low-temperature technology are subject to the EU F-Gas Regulation. Currently, high GWP refrigerants are permitted until at least 2030 due to the exception of Article 13 of the F-Gas Regulation. Due to climate policy goals, operators will be faced with further restrictions on the use of refrigeration systems with a high GWP in the coming years. Among other things, the -50 °C exception when using high GWP refrigerants is increasingly being criticized and possible phase-downs are being proposed. In order to continue to ensure production reliability, strategic decisions must be made at an early stage and investments must be made in future-proof technologies. Anyone who is currently investing in new systems and retrofits with a high GWP (e.g. R452A) runs the risk of no longer being able to operate their systems after 2030, since either maintenance is prohibited or the availability of the refrigerants decreases sharply and the costs for maintenance increase significantly. In the long term, future-proof technologies will be solutions with natural refrigerants, because on the one hand they are environmentally friendly and efficient and on the other hand they are free of any regulations. For applications below -50 °C, cold air cooling technology and cascade systems with flammable refrigerants have become established and are already being used safely in many applications. In addition to new systems, the existing systems must also be considered. Many systems can be equipped with a retrofit of the refrigeration side without changing the actual process.

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  • Avoid supply bottlenecks!

    Early action is essential, as as soon as further restrictions are imposed, all plant operators will be affected and act at the same time.

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