The history of refrigerant industry

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Refrigeration history and the development of refrigeration equipment are very practical in nature. As early as the 17th century, people noticed in day-to-day contexts that a solution of salt and water had cooling properties. In Finland, ice had naturally been used for storage and cooling purposes for centuries.

The first “refrigerators” were loaded with blocks of ice extracted from frozen bodies of water. Most commonly, these were piles of sawdust with supporting boards on the sides or ice cellars. Mounds of saw dust and ice were used in rural areas up to the 1960s.

The first refrigeration equipment

The first known form of artificial refrigeration was invented by the academia, however, at the University of Glasgow in 1748. Unfortunately, this ingenious innovation by William Cullen was not viable for any practical purposes. The solution generated cooling power by evaporating ether in negative pressure. The method was not economical, since it did not recondense the vaporised ether.

Ice refrigeration was patented in America in 1793. In the invention developed by Thomas Moore, the icebox was insulated with charcoal. A compartment in the cover was filled with ice and salt. The compartment was additionally insulated by wrapping in fabric.

In 1805, the American inventor Oliver Evans designed what was, in theoretical terms, the first cooling machine prototype that utilised evaporation and condensation. However, it was not until 1834 that Jacob Perkins built the first practically operable refrigeration system based on this principle, using ether as the refrigerant.

Refrigeration history details of ten years later

Ten years later, an American doctor named John Gorrie developed a cooler based on Oliver Evans’ invention. Gorrie used the device to cool air in the patient rooms of yellow fever patients. Gorrie obtained the first patent for mechanical cooling in the United States in 1851. In the 20th century, all mechanical cooling units were various expansions of John Gorrie’s 50-year-old invention. The only thing missing at the time was a satisfactory refrigerant.

In the same year, in 1851, a wooden cabinet lined with zinc sheets was introduced at the Great Exhibition held in London. The ice cooled the cabinet as it melted. The icebox required continuous and regular maintenance. Iceboxes were used all the way to the 1940s.

Refrigeration history In Finland -comment: Auran Rautateollisuus (ltd.) manufactured Temperator iceboxes, one of which is exhibited at the Finnish Cooling Technology Museum. The famous box is originally from President Risto Ryti’s childhood home.

Air conditioning device for book printing needs

Medical and commercial companies were not the only ones in desperate need of cooling solutions. In 1902, printing houses noticed that printing presses worked less efficiently in hot summer weather.

Postgraduate student Willis Carrier at Cornell University installed the first modern air conditioning device in a colour copying machine. He would later develop a centrifugal compressor for a cold tank. It became a standard in the refrigeration industry for the next two decades.

The world’s first hermetically sealed cooling machine was invented in France in 1905. The sphere refrigeration was invented by Professor of Physics Abbe Audiffren. The machine featured a separate motor, but all the other components were enclosed within two spheres. The refrigerant was sulphur dioxide.

At the Finnish Cooling Technology Museum, you can see the actual Audiffren sphere mechanism, which was used in Hotel Torni from 1931 to 1980.

Refrigeration history: Use of refrigerants 1910–1920

All tested and used refrigerants had, and still have, a variety of harmful effects that require management, including flammability, corrosion and toxicity. Carbon dioxide solved most of the problems but this increased the size of the equipment and the susceptibility to leaks. Improvements were needed to make safe domestic and commercial cooling possible.

The hotel and restaurant sector had also emerged as a sizeable market for refrigeration equipment. Correspondingly, ammunition factories required cooling during World War I. Allied battleships also featured carbon dioxide units that were used to maintain a stable temperature in spaces where ammunition was stored.

The breakthrough of the 1920s and the development refrigerators

Refrigeration history in the 1920s: the domestic refrigerator became an important kitchen appliance. In 1921, roughly 5,000 mechanical refrigerators were already manufactured in the United States, for example. Over the next decade, the number rocketed to a million, gradually making the refrigerator a staple of every household.

The absorption refrigerator was invented in 1922

It generates cooling power through the absorption of vapour into liquid. The refrigerant was a solution of water and either ammonia or lithium bromide. The invention developed by Baltzar von Platen and Carl Munters ran on electricity, gas or paraffin oil. It had no moving parts and was silent. Electrolux purchased the invention and developed it for retail in 1925. The solution was still used in the 1970s in caravans and boats.

Refrigerators themselves did not change much over the years, but there were many leaps in refrigerants. In 1921, Clarence Birdseye invented a method of quick freezing. By 1923, there were dozens of companies manufacturing refrigerators. They used toxic and/or flammable materials, such as sulphur dioxide, chloromethane or ammonia gases to generate cooling power.

In mechanical refrigerators that featured a compressor, a small electric motor drives the pump, i.e. the compressor, which compresses the refrigerants back to its liquid form. In Finland, G. Hartmannin Koneliike Oy sold General Motors’ Frigidaire refrigerators starting from 1928.

Refriferation history: Refrigerators to Finland

Strömberg also developed a refrigerator prototype, in which the electric motor was located on top. Its production was discontinued quite quickly. Frigator, Morus and Mercantile imported refrigerators to Finland from the United States. After the wars, the manufacture of refrigerators in Finland was based on Finnish-made wood frames in which refrigeration systems licensed from abroad were installed.

Freezers, which involve more machinery and power, were also developed in the 1930s and became commonplace in Finland in the 1960s.

In the 1920s, the use of cooling in ventilation advanced by leaps and bounds, and it began to be more widely used in cinemas, hotels and shops, for example, and later in office buildings.

Fluorocarbon trademarked in the 1930s

Researchers first separated elementary fluorine as early as 1886. In 1930 at the annual meeting of the Chemical Society of Atlanta, Thomas Midgley of Frigidaire presents a safer, more powerful and non-flammable refrigerant, chlorofluorocarbon CFC-12. A year later, CFC-12 begins to be used as a commercial refrigerant.

DuPont and General Motors join forces to form Kinetic Chemicals, Inc. In 1930, DuPont registers Freon® as the trademark for chlorofluorocarbon at the DuPont facility in Deepwater, N.J. A year down the line, Freon® 12 is manufactured commercially and used by the entire refrigeration industry. In medicine, Freon is, at the time, used to freeze blood plasma, for example.

In the coming years, several commercial types of freon are brought to the market: CFC-11, CFC-114, CFC-113 and chlorofluorocarbon HCFC-22.

The first air conditioning units

intended for domestic use are also developed in the early 1930s. The automotive industry had also began to develop air conditioning prototypes, and in 1939 General Motors installs a prototype of the first automatic air conditioning unit in a Cadillac chassis. Some buses are also equipped with air conditioning starting from the mid-1930s – mainly for the sake of testing.

Refrigeration history topic in the 40s: cooling cars!

Before the 1940s, opening the window is the only way to cool the interior of a car. At the start of the decade, Packard and Cadillac begin to offer air conditioning systems in their luxury cars mainly in the American Southwest.

CFC-13 was developed in 1945. The incremental cooling of fresh air and the diaphragm valve kick off a trend that eventually leads to modern car air conditioning. Air conditioning units for housing also began to become more commonplace.

After World War II, numerous new companies emerge on the chlorofluorocarbon market and product development flourishes. DuPont releases its registered refrigerant numbering system for general use to prevent product name confusion in the field.

The mass production of modern refrigerators also begins to pick up after the Second World War.

Development of aerosols in the 1950s and 60s

In the 1950s, room heating and cooling units are developed, but the early models are large and expensive. CFC-14 is introduced in 1955 (e.g. aerosol pesticide bottles). In the mid-1960s, more than half of all fluorocarbons produced go into the production of aerosols.

CFC-502 is also introduced as a commercial refrigerant, which is packed into light cylinders to improve safety and facilitate handling in supermarkets, for example. Freon® 13, which is used for ultra-low temperature cooling (-100°C and lower), enters the market.

By 1967, 40% of new cars feature factory-fitted air conditioning. A year later, it comes as standard in all higher-end American-made cars. The demand for fluorocarbons in Europe, as well, increases considerably.

Refrigeration history of the 1970s and the energy crisis

In the 1970s, the “energy crisis” leads to the development of energy-efficient air conditioning.

In the United States, DuPont begins the development of its own alternative refrigerants in response to the discussion about the possible harmful effects of fluorocarbons. The first product developed by DuPont is hydrofluorocarbon (HFC)-134a, which is non-flammable, safer to use and better for the ozone layer, because it does not contain chlorine.

Mario Molina and Sherry Rowland publish their ozone layer theory in 1974. It strongly suggests that the continuous use of CFC compounds may deteriorate the ozone layer. This is more than a decade before an actual scientific study on the issue is conducted.

The air conditioning systems of cars are developed towards increased lightness, power and compactness. The automotive industry becomes cognisant of the concerns regarding ozone depletion. By 1976, HFC-134a is regarded as a refrigerant to replace CFC-12, leading to a decrease in aerosol production.

Refrigeration history: The changing environment and the 1980s and 90s

In 1980, 72% of new cars sold in the United States feature air conditioning. Within ten years, the number climbs to 94%.

In 1985, an “ozone hole” is discovered above the Antarctic, but its cause is unclear. Agreements on international collaboration related to research on the ozone layer are laid down in the Vienna Convention. The aim is to support research concerning the state of the ozone layer, monitor the production of CFC compounds and promote information exchange between nations.

As a result of the situation and the Vienna Convention, the Montreal Protocol is signed in 1987, requiring CFC consumption to be reduced by 50% over the next ten years. The agreement has been supplemented numerous times thereafter.

In March 1988

a group of specialists working under the international Ozone Trends panel publishes a summary on CFC compounds, which links the ozone hole and possible seasonal ozone depletions in the northern hemisphere.

Within ten days, DuPont’s production facility, among others, undertakes to an incremental discontinuation of CFC production by transitioning to other alternatives that are safe to use, environmentally friendly and only require minor equipment modifications.

Due to the impending phaseout of CFC-12, car manufacturers begin to use refrigerant HFC-134a, which does not deteriorate the ozone layer. In addition to this, the refrigeration industry begins to develop new components, such as condensers and compressors, as well as new lubricants and dehumidifiers.

Alternative refrigerants – the first product family

Due to the aforementioned agreements and the resulting legislative changes, a gradual transition away from CFC compounds begins. There is more development, testing and commercialisation of more environmentally friendly refrigerants.

Among other manufacturers, DuPont spends hundreds of millions of dollars in development, ensuring that the first alternative refrigerants become commercially available within four years. DuPont’s family of Suva® refrigerants is launched in January 1991. These products with low or no ozone depletion potential are called HCFC and HFC compounds.

By 1994, Suva® refrigerants become a globally accepted, more ecological alternative to CFC compounds, which have been the backbone of the refrigeration and air conditioning industry for more than 60 years.

Refrigerants in the 2000s and beyond

In the 2000s, many substitutive ozone-friendly refrigerants have been developed for use in both retrofitting and new systems. The development is still ongoing to ensure that the goals of the Montreal Protocol are reached within the agreed schedule.

Low ODP (Ozone Depletion Potential) and GWP (Global Warming Potential) values can be achieved by means of a variety of tested mixtures. This often involves the management of an undesirable attribute, such as flammability or combustion properties. This also imposes new requirements on refrigerant tanks, bottles, equipment, installation, fitter expertise, qualifications, training and transport, for example.

Goals

Within the European Union, too, the goal is to implement a phased transition towards more environmentally friendly refrigerants. The production of new CFC plants has been banned in the EU since 1995. Moreover, the installation of new HCFC systems has been prohibited since the early 2000s. The use of recovered/recycled HCFC refrigerant was permitted until the end of 2014. Its use is permitted in absolutely necessary and critical plants only.

Going forward, the intention is to move towards more natural refrigerants. Restrictions are also on the cards for HFC refrigerants starting from the early 2020s.

The European Union’s new F-gas Regulation

affects the refrigeration field and the use of certain refrigerants in particular. From the beginning of 2017, the impact has been stronger due to the price hikes and declined availability. This is the result of refrigerant quotas, which necessitate the distribution of the volumes of new refrigerants sold on the EU markets among the various operators. The quotas will continue to decrease in size until 2030.

The F-gas Regulation has had the most substantial impact on the use of refrigerants with the highest GWP, such as R404 and R410, as well as certain refrigerant mixtures. Refrigerant manufacturers have also reported reductions and cessations in production and deliveries. The scarcity maintains high price levels.