2,3,3,3-Tetrafluoropropene Explained

2,3,3,3-Tetrafluoropropene, HFO-1234yf, is a hydrofluoroolefin (HFO) with molecular formula CH2=CFCF3. Its primary application is as a refrigerant with low global warming potential (GWP).

As a refrigerant, it is designated R-1234yf[1] and marketed under the names Opteon YF by Chemours and as Solstice YF by Honeywell.[2] R-1234yf is also a component of zeotropic refrigerant blend R-454B.

HFO-1234yf has a GWP less than carbon dioxide, itself 1,430 times less potent than R-134a. For this reason, 2,3,3,3tetrafluoropropene is the pre-eminent replacement for R-134a in vehicular air conditioners. As of 2022, 90% of new U.S. vehicles are estimated to use HFO-1234yf.[3] Unlike previous vehicular refrigerants, 2,3,3,3tetrafluoropropene is flammable, but does not increase fire risk in internal combustion engines.

One drawback is it breaks down into short-chain perfluorinated carboxylic acids (PFCAs), which are persistent organic pollutants.[4]

Adoption by automotive industry

HFO-1234yf was developed by a team at DuPont, led by Barbara Haviland Minor, jointly with researchers at Honeywell.[5] [6] Their goal was to meet European directive 2006/40/EC, which went into effect in 2011 and required that all new car platforms for sale in Europe use a refrigerant in its AC system with a global warming potential (GWP) less than 150 times more potent than carbon dioxide.[7] HFO-1234yf was initially considered to have a 100-year GWP of 4, and is now considered to have a 100-year GWP lower than 1 (carbon dioxide has a GWP of 1.0).[8] [9]

Among the alternatives developed to comply with 2006/40/EC, HFO-1234yf had the lowest switching cost for automakers.[10] [11] It can be used as a "near drop-in replacement" for R-134a,[12] the previous automobile AC refrigerant, which has a 100-year GWP of 1430.[13] [14] HFO-1234yf can be handled in repair shops in the same way as R-134a, although it requires some different, specialized equipment to perform the service. One of the reasons for that is the flammability of HFO-1234yf.[15] Another issue affecting the compatibility between HFO-1234yf and R-134a-based systems is the choice of lubricating oil.[16]

On July 23, 2010, General Motors announced that it would introduce HFO-1234yf in 2013 Chevrolet, Buick, GMC, and Cadillac models in the U.S.[17] Shortly thereafter, Honeywell and DuPont announced that they would jointly build a manufacturing facility in Changshu, Jiangsu Province, China to produce HFO-1234yf.[18] In 2012, Cadillac produced the first American car using R-1234yf.[19] Since then, Chrysler,[20] GMC[21] and Ford[22] have all begun transitioning vehicles to R1234yf.

Japanese automakers are also transitioning to R1234yf. Honda and Subaru began to introduce the new refrigerant with the 2017 models. From 2017 to 2018, BMW changed all of its models to R-1234yf. As of 2018, 50% of new vehicles from original equipment manufacturers (OEMs) are estimated to use R-1234yf.[23]

In 2017, Honeywell opened a new plant in Geismar, Louisiana, to handle increased demand for the compound.[24] [25] Honeywell and DuPont hold most patents issued for HFO-1234yf and remained the pre-eminent manufacturers in 2018.[26]

Flammability

Although the product is classified slightly flammable by ASHRAE, several years of testing by SAE International proved that the product could not be ignited under conditions normally experienced by a vehicle.[27] Tests conducted in 2008 indicated that ignition requires temperatures exceeding 900C and mixture with PAG oil.[28] Once in flame, 2,2,3,3trifluoropropene releases highly corrosive and toxic gaseous hydrogen fluoride and carbonyl fluoride.[29]

In August 2012, Mercedes-Benz showed that the substance ignited in simulated head-on collisions. A senior Daimler engineer who ran the tests, stated "We were frozen in shock, I am not going to deny it. We needed a day to comprehend what we had just seen." When researchers sprayed 2,2,3,3trifluoropropene and A/C compressor oil onto a car's hot engine, the mixture burned in two out of three times.[30] In September, Daimler issued a press release, proposed a recall of cars using the refrigerant, and continued to use older refrigerants in its own designs.[31] The German automakers argued for development of carbon dioxide refrigerants, which they argued would be safer.

In October 2012, SAE International established a new Cooperative Research Project, CRP1234-4, to extend its previous testing and investigate Daimler's claims. The investigation concluded that R-1234yf did not increase the estimated risk of vehicle fire exposure, because "the refrigerant release testing completed by Daimler was unrealistic" and "created extreme conditions that favored ignition".[32] Germany's also conducted its own tests. In their August 2013 report to the European Union, the KBA concluded that while R-1234yf was potentially more hazardous than R-134a, it did not constitute a serious danger.

Writing for Auto Service Professional, Gordon Jacques summarized the controversy:

Mixing HFO-1234yf with 10–11% R-134A is in development to produce a hybrid gas under review by ASHRAE for classification as A2L which is described as "virtually non-flammable". These gases are under review with the names of R451A and R451B. These mixes have GWP of ~147.[33]

Other additives have been proposed for lowering the flammability of HFO-1234yf, such as trifluoroiodomethane, which has a low GWP due to its short atmospheric lifetime, but is slightly mutagenic.[34]

In the environment

HFO-1234yf has been shown to atmospherically transform into trifluoroacetic acid (TFA), leading to a potential for wet and dry atmospheric deposition.[35] [36]

See also

Notes and References

  1. News: Sciance . Fred . The Transition from HFC- 134a to a Low -GWP Refrigerant in Mobile Air Conditioners HFO -1234yf . 1 August 2018 . General Motors Public Policy Center . October 29, 2013.
  2. News: Honeywell and Chemours Announce New Manufacturing Plants for HFO 1234yf . 26 July 2018 . Aspen Refrigerants . June 12, 2017 . 4 August 2020 . https://web.archive.org/web/20200804000821/https://www.aspenrefrigerants.com/news/all/honeywell-and-chemours-announce-new-manufacturing-plants-hfo-1234yf . dead .
  3. Web site: StackPath . 2022-05-28 . www.vehicleservicepros.com. 23 March 2022 .
  4. Wang . Ziyuan . Wang . Yuhang . Li . Jianfeng . Henne . Stephan . Zhang . Boya . Hu . Jianxin . Zhang . Jianbo . Impacts of the Degradation of 2,3,3,3-Tetrafluoropropene into Trifluoroacetic Acid from Its Application in Automobile Air Conditioners in China, the United States, and Europe . Environmental Science & Technology . 30 January 2018 . 52 . 5 . 2819–2826 . 10.1021/acs.est.7b05960. 29381347 . 2018EnST...52.2819W .
  5. Web site: Recognizing excellence: Development of HFO-1234yf as the next generation refrigerant for the automotive industry . 2010 DuPont Excellence Awards Sustainable Growth . 31 July 2018. 3. 2010.
  6. DuPont Names Seven New DuPont Fellows . 30 July 2018 . DuPont Media Center . July 17, 2014. https://web.archive.org/web/20180730170851/http://www.dupont.com/corporate-functions/media-center/press-releases/dupont-names-seven-new-dupont-fellows.html. 30 July 2018. dead.
  7. Web site: Directive 2006/40/EC of the European Parliament and of the Council of 17 May 2006 relating to emissions from air-conditioning systems in motor vehicles and amending Council Directive 70/156/EEC . EFCTC . 26 July 2018 . 26 July 2018 . https://web.archive.org/web/20180726234049/https://www.fluorocarbons.org/mac-directive-402006/ . dead .
  8. News: IPCC confirms HFO GWPs are less than 1 . 26 July 2018 . Cooling Post . 3 Feb 2014.
  9. Book: Scientific Assessment of Ozone Depletion: 2014 Full Report . 2014 . World Meteorological Organization Global Ozone Research and Monitoring Project—Report No. 55 . 551 .
  10. Ansari . Naushad A. . Yadav . Bipin . Kumar . Jitendra . August 2013 . Theoretical exergy analysis of HFO-1234yf and HFO-1234ze as an alternative replacement of HFC-134a in simple vapour compression refrigeration system . International Journal of Scientific & Engineering Research . 4 . 8 . 10.1.1.415.9796.
  11. HFO-1234yf, New Dawn of Refrigerant Alternatives . 1 August 2018 . JARN: Japan Air Conditioning, Heating & Refrigeration News . April 25, 2008 . 40 . 4 . 1, 6, 24.
  12. Honeywell's low-global-warming refrigerant for vehicles approved for import, use by Japan regulators . 26 July 2018 . Honeywell . August 4, 2009.
  13. Book: P. Forster. V. Ramaswamy. P. Artaxo. T. Berntsen. R. Betts. D.W. Fahey. J. Haywood. J. Lean. D.C. Lowe. G. Myhre. J. Nganga. R. Prinn. G. Raga. M. Schulz. R. Van Dorland. Solomon. S.. Miller. H.L.. Tignor. M.. Averyt. K.B.. Kristen Averyt. Marquis. M.. Chen. Z.. Manning. M.. Qin. D.. Climate Change 2007: the physical science basis. Contribution of Working Group I to the fourth assessment report of the Intergovernmental Panel on Climate Change. 2007. Cambridge University Press. Cambridge, United Kingdom and New York, NY, USA. en. Chapter 2: Changes in atmospheric constituents and in radiative forcing. https://www.ipcc.ch/publications_and_data/ar4/wg1/en/ch2.html. 9 October 2016. 1 December 2016. https://web.archive.org/web/20161201152606/http://www.ipcc.ch/publications_and_data/ar4/wg1/en/ch2.html. dead.
  14. Web site: Air conditioning in new vehicle models requires a greener gas . 26 July 2018 . Autodata . 2017.
  15. News: Gordon . Jacques . April 12, 2017 . Real world experience with R1234yf: The new refrigerant is finally here; are you ready? . 26 July 2018 . Auto Service Professional.
  16. News: Johnson . Alec . Understanding refrigerant oils . 26 July 2018 . Refrigerant HQ . October 13, 2017.
  17. GM first to market greenhouse gas-friendly air conditioning refrigerant in U.S. . 26 July 2018 . GM Corporate Newsroom . 2010-07-23.
  18. "Automakers Go HFO", Chemical & Engineering News, July 26, 2010
  19. News: Schaeber . Steve . February 27, 2017 . R-1234yf at the 2017 PHL Auto Show . 26 July 2018 . MACS Worldwide.
  20. David . Zatz . Chrysler adopting R1234YF . October 1, 2013 . Allpar News . 2018-06-16 . en-US.
  21. News: September 22, 2016 . GMC hits the road with R-1234yf . 26 July 2018 . MACS Worldwide.
  22. News: Schaeber . Steve . August 17, 2016 . Ford dealers selling their first MPVs with R-1234yf . 26 July 2018 . MACS Worldwide.
  23. News: May 15, 2018 . Ask the expert: How many light duty OEs use HFO-1234yf refrigerant? . 26 July 2018 . Vehicle Service Pros.
  24. Honeywell announces major investments to increase HFO-1234yf production in the United States . 26 July 2018 . Honeywell . December 10, 2013 . 26 July 2018 . https://web.archive.org/web/20180726235518/https://www.honeywell.com/newsroom/pressreleases/2013/12/honeywell-announces-major-investments-to-increase-hfo-1234yf-production-in-the-united-states . dead .
  25. Honeywell starts up $300 million automotive refrigerant production facility in Louisiana . 26 July 2018 . Honeywell . May 16, 2017.
  26. News: Marwa . Stefen . HFO-1234yf market 2018 global share and projections: Honeywell and Chemours . 26 July 2018 . The Aerospace News . July 26, 2018 . https://web.archive.org/web/20180726235811/https://theaerospacenews.com/hfo-1234yf-market-2018-global-share-and-projections-honeywell-and-chemours/204170/ . 26 July 2018 . dead .
  27. Web site: Lewandowski . Thomas A. . Additional risk assessment of alternative refrigerant R-1234yf prepared for SAE International cooperative research program CRP1234-4 . SAE International . 26 July 2018. July 24, 2013.
  28. Web site: HFO-1234yf Low GWP Refrigerant Update. Spatz. Mark. Minor. Barbara. July 2008.
  29. News: 2014 . Refreshingly cool, potentially toxic . 26 July 2018 . Ludwig-Maximilians-Universität (LMU) Munich.
  30. News: Hetzner . Christiaan . Coolant safety row puts the heat on Europe's carmakers . 26 July 2018 . Reuters . December 12, 2012.
  31. News: Bolduc . Douglas A. . August 8, 2013 . German officials provide mixed ruling on Honeywell refrigerant Despite fire risk, agency does not seek recall of cars using HFO-1234yf . 26 July 2018 . Automotive News Europe. subscription.
  32. News: A heated row over coolants . 26 July 2018 . The Economist . August 31, 2013.
  33. Web site: R134a alternative is "virtually non-flammable". Cooling Post. 30 November 2014 . en-GB. 2017-06-09.
  34. Web site: US6969701B2 Azeotrope-like compositions of tetrafluoropropene and trifluoroiodomethane . Google patents . 26 July 2018.
  35. 10.1021/es902481f . Ozone and TFA Impacts in North America from Degradation of 2,3,3,3-Tetrafluoropropene (HFO-1234yf), A Potential Greenhouse Gas Replacement . 2010 . Luecken . Deborah J. . Waterland . Robert L. . Papasavva . Stella . Taddonio . Kristen N. . Hutzell . William T. . Rugh . John P. . Andersen . Stephen O. . Environmental Science & Technology . 44 . 1 . 343–348 . 19994849 . 2010EnST...44..343L .
  36. Hurley . M.D . Wallington . T.J . Javadi . M.S . Nielsen . O.J . 2008 . Atmospheric chemistry of CF3CF=CH2: Products and mechanisms of Cl atom and OH radical initiated oxidation . Chemical Physics Letters . 450 . 4–6 . 263–267 . 10.1016/j.cplett.2007.11.051.

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