Trans-1,3,3,3-Tetrafluoropropene

Last updated
trans-1,3,3,3-Tetrafluoropropene
HFO-1234ze.svg
Names
Preferred IUPAC name
(1E)-1,3,3,3-Tetrafluoroprop-1-ene
Other names
R-1234ze(E); HFO-1234ze(E); trans-1,3,3,3-tetrafluoro-1-propene; trans-1,3,3,3-tetrafluoropropylene; trans-1,3,3,3-tetrafluoroprop-1-ene
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.238.116 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 471-480-0
PubChem CID
UNII
  • InChI=1S/C3H2F4/c4-2-1-3(5,6)7/h1-2H/b2-1+ Yes check.svgY
    Key: CDOOAUSHHFGWSA-OWOJBTEDSA-N Yes check.svgY
  • InChI=1/C3H2F4/c4-2-1-3(5,6)7/h1-2H/b2-1+
    Key: CDOOAUSHHFGWSA-OWOJBTEDBQ
  • F[C@H]=CC(F)(F)F
Properties
C3H2F4
Molar mass 114.043 g·mol−1
AppearanceColorless gas [1]
Melting point −156 °C (−249 °F; 117 K) [2]
Boiling point −19 °C (−2 °F; 254 K) [1] [2]
Critical point (T, P)109.4 °C, 36.36 bar [2]
0.373 g/L [1] [2]
Vapor pressure 703 kPa at 310 K
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

trans-1,3,3,3-Tetrafluoropropene, HFO-1234ze(E-isomer), is a hydrofluoroolefin that has the same chemical formula as HFO-1234ze(Z-isomer) and one of many tetrafluoropropene isomers. [3] The HFO-1234ze E-isomer is considered the more useful for refrigeration applications as compared to the HFO-1234ze Z-isomer. It was developed as a "fourth generation" refrigerant intended to replace R-134a, as a blowing agent for foam and aerosol applications, in air horns and gas dusters, [4] [5] and planned use in metered-dose inhalers.

Contents

Properties

The structure of trans-1,3,3,3-tetrafluoropropene was investigated both in the gas state (gas electron diffraction) and in the crystalline phase (X-ray diffraction). In the crystal, it aggregates via C-H---F contacts from 2.44(1) to 2.63(1) Å. [6] Combustion experiments with trans-1,3,3,3-tetrafluoropropene produce carbon dioxide, carbonyl fluoride and hydrogen fluoride as the main combustion products. The determination of the flammability range leads to the classification of trans-1,3,3,3-tetrafluoropropene as a highly flammable gas.

Production

Catalytic dehydrofluorination of HFC-245fa produces a mixture of both E and Z-isomer of R-1234 [7] ; by adjusting the catalyst Z-isomer concentration varies between 15% to 23%. [8]

Dehydrofluorination of liquid phase HFC-245fa using aqueous solutions of caustic or other strong bases produces a mixture of both E and Z-isomers of R-1234; by adjusting the reaction temperature varies the Z-isomer concentration between 13% to 15%. [9]

The E-isomer is considered the most useful for refrigeration applications so after separation of the E-isomer from the Z-isomer in the above listed processes, the Z-isomer can be isomerized to the E-isomer in a separate step or the Z-isomer can be converted back to HFC-245fa by adding hydrogen fluoride in a separate step. [10] Once returned to HFC-245fa, the above production steps repeated to increase the volume of desired E-isomer.

Uses

The increasing concerns about global warming and the related possible undesirable climate effects have led to an increasing agreement in developed countries for the reduction of greenhouse gas emissions. Given the relatively high global warming potential of most of the hydro-fluoro-carbons (HFCs), several actions are ongoing in different countries to reduce the use of these fluids. For example, the European Union's recent F-Gas regulation [11] specifies the mandatory GWP values of the refrigerants to be used as working fluids in almost all air conditioners and refrigeration machines beginning in 2020. [12]

Several types of possible replacement candidates have been proposed so far, both synthetic and natural. Among the synthetic options, hydro-fluoro-olefins (HFOs) are the ones appearing most promising thus far.

HFO-1234ze(E) has been adopted as a working fluid in chillers, heat pumps, and supermarket refrigeration systems. [13] [14] [15] There are also plans to use it as a propellant in metered-dose inhalers. [16]

It has been demonstrated that HFO-1234ze(E) can not be considered as a drop-in replacement of HFC-134a. In fact, from a thermodynamic point of view, it can be stated that:

– The theoretical coefficients of performance of HFO-1234ze(E) is slightly lower than HFC-134a;

– HFO-1234ze(E) has a different volumetric cooling capacity when compared to HFC-134a.

– HFO-1234ze(E) has saturation pressure drops higher than HFC-134a during two-phase heat transfer under the constraint of achieving the same heat transfer coefficient. [17]

So, from a technological point of view, modifications to the condenser and evaporator designs and to compressor displacement are needed to achieve the same cooling capacity and energetic performance of HFC-134a. [12]

Environmental impact

The use of R-134a is being phased out because of its high global warming potential (GWP). HFO-1234ze(E) itself has zero ozone-depletion potential (ODP=0), a very low global warming potential (GWP < 1 ), even lower than CO2, and it is classified by ANSI/ASHRAE [18] as class A2L refrigerant (lower flammability (see below) and lower toxicity). [19]

In open atmosphere however, it has been suggested in a UNSW study that HFO-1234ze can form HFC-23 as one of its secondary atmospheric breakdown products. HFC-23 is a very potent greenhouse gas with a GWP100 of 14,800. This could make the secondary GWP of R-1234ze in the range of 1,400±700 considering the amount of HFC-23 which may form from HFO-1234ze in the atmosphere. [20] [21] The findings of the study are however contradicted in other papers. [22]

Besides the global warming potential, when HFOs decompose in the atmosphere, trifluoroacetic acid(TFA) is formed, which also remains in the atmosphere for several days. The trifluoroacetic acid then forms sodium trifluoroacetate, a salt of trifluoroacetic acid, in water and on the ground. Due to high polarity and low degradability, it is difficult to remove TFA salts from drinking water (ICPR 2019). [23] [24] However, the amount of TFA salts potentially generated in applications such as metered-dose inhalers has been estimated to be negligible. [25]

See also

References

  1. 1 2 3 "MSDS Resource Centre". msds-resource.honeywell.com.
  2. 1 2 3 4 Solstice® ze Refrigerant (HFO-1234ze) : Low GWP Hydrofluoroolefins (HFO) : The Environmental Alternative to Traditional Refrigerants, Honeywell Belgium N.V., FPR-003/2015-01. Accessed 2024-01-05.
  3. ↑ Schwabedissen, Jan; Glodde, Timo; Vishnevskiy, Yury V.; Stammler, Hans-Georg; Flierl, Lukas; Kornath, Andreas J.; Mitzel, Norbert W. (September 2020). "Structures and Properties of trans-1,3,3,3-Tetrafluoro- propene (HFO-1234ze) and 2,3,3,3-Tetrafluoropropene (HFO-1234yf) Refrigerants". ChemistryOpen. 9 (9): 921–928. doi:10.1002/open.202000172. ISSN   2191-1363. PMC   7469860 . PMID   32913699.
  4. ↑ Honeywell Sells Novel Low-Global-Warming Blowing Agent To European Customers Archived 2016-03-03 at the Wayback Machine , Honeywell press release, Oct. 7, 2008
  5. ↑ "1234ZE brochure" (PDF).
  6. ↑ Jan Schwabedissen, Timo Glodde, Yury V. Vishnevskiy, Hans‐Georg Stammler, Lukas Flierl, Andreas J. Kornath, Norbert W. Mitzel: Structures and Properties of trans ‐1,3,3,3‐Tetrafluoro‐ propene (HFO‐1234ze) and 2,3,3,3‐Tetrafluoropropene (HFO‐1234yf) Refrigerants. In: ChemistryOpen. Band 9, Nr. 9, September 2020, ISSN 2191-1363, S. 921–928, doi:10.1002/open.202000172
  7. ↑ US9302962B2,Peng, Sheng&Nappa, Mario Joseph,"Dehydrofluorination of 245fa to 1234ze",issued 2016-04-05
  8. ↑ US12416431B2,Peng, Sheng&Nappa, Mario Joseph,"HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions",issued 2025-09-16
  9. ↑ US12416431B2,Peng, Sheng&Nappa, Mario Joseph,"HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions",issued 2025-09-16
  10. ↑ US12416431B2,Peng, Sheng&Nappa, Mario Joseph,"HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions",issued 2025-09-16
  11. ↑ Regulation (EU) No 517/2014
  12. 1 2 Giulia Righetti, Claudio Zilio, Simone Mancin & Giovanni A. Longo (2016): A review on in-tube two-phase heat transfer of hydro-fluoro-olefines refrigerants, Science and Technology for the Built Environment, DOI:10.1080/23744731.2016.1229528
  13. ↑ Longo, Giovanni A.; Zilio, Claudio; Righetti, Giulia; Brown, J. Steven (2014). "Condensation of the low GWP refrigerant HFO1234ze(E) inside a Brazed Plate Heat Exchanger". International Journal of Refrigeration. 38: 250–259. doi:10.1016/j.ijrefrig.2013.08.013.
  14. ↑ Longo, Giovanni A.; Mancin, Simone; Righetti, Giulia; Zilio, Claudio (2016). "HFO1234ze(E) vaporisation inside a Brazed Plate Heat Exchanger (BPHE): Comparison with HFC134a and HFO1234yf". International Journal of Refrigeration. 67: 125–133. doi:10.1016/j.ijrefrig.2016.04.002.
  15. ↑ Longo, Giovanni A.; Mancin, Simone; Righetti, Giulia; Zilio, Claudio (2016). "Saturated flow boiling of HFC134a and its low GWP substitute HFO1234ze(E) inside a 4 mm horizontal smooth tube". International Journal of Refrigeration. 64: 32–39. doi:10.1016/j.ijrefrig.2016.01.015.
  16. ↑ "AstraZeneca partners with Honeywell on development of HFO-1234ze MDIs". www.oindpnews.com.
  17. ↑ Brown, J.S., C. Zilio, R. Brignoli, and A. Cavallini. 2013. Heat transfer and pressure drop penalization terms (exergy losses) during flow boiling of refrigerants. International Journal of Energy Research 37:1669–79.
  18. ↑ ANSI/ASHRAE Standard 34, 2010. Designation and Safety Classification of Refrigerants.
  19. ↑ "The environmental alternative to traditional refrigerants". Honeywell. 2015. p. 2.
  20. ↑ McGillen, Max (December 11, 2023). "Ozonolysis can produce long-lived greenhouse gases from commercial refrigerants". Proceedings of the National Academy of Sciences. 120 (51) e2312714120. Bibcode:2023PNAS..12012714M. doi: 10.1073/pnas.2312714120 . PMC   10742373 . PMID   38079548.
  21. ↑ Hansen, Christopher (February 5, 2023). "Photodissociation of CF3CHO provides a new source of CHF3 (HFC-23) in the atmosphere: implications for new refrigerants". doi:10.21203/rs.3.rs-199769/v1.
  22. ↑ "Refrigerant Degradation: Is HFC-23 (CF3H) formed due to the decomposition of HFOs and HCFOs in the troposphere?" (PDF). EFCTC. 2021.
  23. ↑ Kauffeld, Michael (June 11, 2021). "Environmental impact of HFO refrigerants & alternatives for the future". Global Access Government.
  24. ↑ van der Hoff, Menno (October 3, 2022). "Onderzoek toont zorgwekkende toename van TFA als afbraakproduct van HFK's en HFO's".
  25. ↑ Tewari, Shivendra G.; Bell, John P.; Budgen, Nigel; Platz, Stefan; Gibbs, Megan; Newham, Peter; Kimko, Holly (November 30, 2023). "Pressurized metered-dose inhalers using next-generation propellant HFO-1234ze(E) deposit negligible amounts of trifluoracetic acid in the environment". Frontiers in Environmental Science. 11 1297920. Bibcode:2023FrEnS..1197920T. doi: 10.3389/fenvs.2023.1297920 .
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