Thermal Decomposition and Oxidative Decomposition Mechanism of HFC-134a by Experimental and DFT Method

XU Yunting, ZHANG Kai, DAI Xiaoye, SHI Lin

热科学学报 ›› 2024, Vol. 33 ›› Issue (5) : 1990-2003.

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热科学学报 ›› 2024, Vol. 33 ›› Issue (5) : 1990-2003. DOI: 10.1007/s11630-024-1981-5  CSTR: 32141.14.JTS-024-1981-5

Thermal Decomposition and Oxidative Decomposition Mechanism of HFC-134a by Experimental and DFT Method

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Thermal Decomposition and Oxidative Decomposition Mechanism of HFC-134a by Experimental and DFT Method

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摘要

鉴于《蒙特利尔议定书》基加利修正案和全球范围内的低碳减排环保要求,大量HFCs制冷剂亟待淘汰和降解,因此高效且温和的降解方法变得至关重要。本研究以典型的氢氟烃制冷剂HFC-134a为对象,采用实验与量子化学密度泛函理论(DFT)模拟相结合的方法,深入探讨了其热分解和氧化热解路径。量子化学模拟结果显示,在热分解过程中,起始反应化学键的断裂成为决速步骤,且最易生成的可检测到的闭壳层产物包括CF2=CHF、HF、CH3F、CHF3、CH2F2、CF4等。活性氧化物能显著降低HFC-134a分解的自由能垒。为实现HFC-134a的高效降解,应开发和选择适当的催化剂以提高反应体系中活性氧物质的水平。实验研究进一步证实,在不同温度(240°C至360°C)和压力(0.1 MPa至4.5 MPa)条件下,HFC-134a可能通过不同反应路径实现降解,这一结果与模拟预测保持一致。

Abstract

In response to the Kigali Amendment to the Montreal Protocol and global low-carbon emission environmental requirements, the phase-out and decomposition of numerous HFC refrigerants have become urgent, necessitating efficient and mild decomposition methods. This study investigates the thermal decomposition and oxidative thermal decomposition pathways of the typical hydrofluorocarbon refrigerant HFC-134a, employing a combination of experimental and quantum chemical DFT simulation methods. Quantum chemical simulations reveal that the initial reaction bond cleavage serves as the rate-determining step during the thermal decomposition process, with the most easily detectable closed-shell products including CF2=CHF, HF, CH3F, CHF3, CH2F2, and CF4. Reactive oxygen species can significantly reduce the Gibbs free energy barrier for HFC-134a decomposition. To achieve efficient degradation of HFC-134a, appropriate catalysts should be developed and selected to increase the level of reactive oxygen species in the reaction system. Experimental studies further corroborate that HFC-134a may undergo degradation through distinct reaction pathways under varying temperature (240°C to 360°C) and pressure (0.1 MPa to 4.5 MPa) conditions, in agreement with simulation predictions.

关键词

HFC-134a / pyrolysis / oxidative thermal decomposition / DFT / refrigerant

Key words

HFC-134a / pyrolysis / oxidative thermal decomposition / DFT / refrigerant

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XU Yunting , ZHANG Kai , DAI Xiaoye , SHI Lin. Thermal Decomposition and Oxidative Decomposition Mechanism of HFC-134a by Experimental and DFT Method[J]. 热科学学报, 2024, 33(5): 1990-2003 https://doi.org/10.1007/s11630-024-1981-5
XU Yunting , ZHANG Kai , DAI Xiaoye , SHI Lin. Thermal Decomposition and Oxidative Decomposition Mechanism of HFC-134a by Experimental and DFT Method[J]. Journal of Thermal Science, 2024, 33(5): 1990-2003 https://doi.org/10.1007/s11630-024-1981-5

参考文献

[1] Alimonti G., Mariani L., Prodi F., Ricci R.A., A critical assessment of extreme events trends in times of global warming. The European Physical Journal Plus, 2022, 137(1): 1–20.
[2] Shuai C., Shen L., Jiao L., Wu Y., Tan Y., Identifying key impact factors on carbon emission: Evidences from panel and time-series data of 125 countries from 1990 to 2011. Applied Energy, 2017, 187: 310–325.
[3] Rao S., Riahi K., The role of non-CO2 greenhouse gases in climate change mitigation: long-term scenarios for the 21st century. The Energy Journal, 2006, 27(3): 177–200.
[4] Savitha D.C., Ranjith P.K., Talawar B., Rana Pratap Reddy N., Refrigerants for sustainable environment–a literature review. International Journal of Sustainable Energy, 2022, 41(3): 235–256. 
[5] Heredia-Aricapa Y., Belman-Flores J.M., Mota-Babiloni A., Serrano-Arellano J., García-Pabón J.J., Overview of low GWP mixtures for the replacement of HFC refrigerants: R134a, R404A and R410A. International Journal of Refrigeration, 2020, 111: 113–123.
[6] Kumma N., Kruthiventi S.S.H., Thermodynamic performance and flammability studies of hydrocarbon based low global warming potential refrigerant mixtures. Journal of Thermal Science, 2022, 31(5): 1487–1502.
[7] Aprea C., Greco A., Maiorino A., HFOs and their binary mixtures with HFC134a working as drop-in refrigerant in a household refrigerator: Energy analysis and environmental impact assessment. Applied Thermal Engineering, 2018, 141: 226–233.
[8] Yana M.S., Domanski P., Low-GWP refrigerants status and outlook. USDOE Office of Energy Efficiency and Renewable Energy, United States, 2022.
[9] Shuai C., Shen L., Jiao L., Wu Y., Tan Y., Identifying key impact factors on carbon emission: Evidences from panel and time-series data of 125 countries from 1990 to 2011. Applied Energy, 2017, 187: 310–325.
[10] Heath E.A., Amendment to the Montreal protocol on substances that deplete the ozone layer (Kigali amendment). International Legal Materials, 2017, 56(1): 193–205.
[11] Velders G.J., Fahey D.W., Daniel J.S., McFarland M., Andersen S.O., The large contribution of projected HFC emissions to future climate forcing. Proceedings of the National Academy of Sciences, 2009, 106(27): 10949–10954. 
[12] ODS Destruction in the United States and Abroad. https://www.epa.gov/sites/default/files/2018-03/documents/ods-destruction-in-the-us-and-abroad_feb2018.pdf/, 2022 (accessed on 8 November 2022).
[13] Dai X., An Q., Xu Y., Shi L., Review of waste refrigerant destruction methods. CIESC Journal, 2021, 72: 1–6.
[14] Sheraz M., Anus A., Le V.C.T., Swamidoss C.M.A., Kim E.K., Kim S., A comprehensive review of contemporary strategies and approaches for the treatment of HFC‐134a. Greenhouse Gases: Science and Technology, 2021, 11(5): 1118–1133.
[15] Iizuka A., Ishizaki H., Mizukoshi A., Noguchi M., Yamasaki A., Yanagisawa Y., Simultaneous decomposition and fixation of F-gases using waste concrete. Industrial & Engineering Chemistry Research, 2011, 50(21): 11808–11814. 
[16] Jeong S., Sudibya G.L., Jeon J.K., Kim Y.M., Swamidoss C.M.A., Kim S., The use of a γ-Al2O3 and MgO mixture in the catalytic conversion of 1, 1, 1, 2-tetrafluoroethane (HFC-134a). Catalysts, 2019, 9(11): 901. 
[17] Andrew Swamidoss C.M., Sheraz M., Anus A., Jeong S., Park Y.K., Kim Y.M., Kim S., Effect of Mg/Al2O3 and calcination temperature on the catalytic decomposition of HFC-134a. Catalysts, 2019, 9(3): 270.
[18] Mi T., Han J., He X., Qin L., Investigation of HFC-134a decomposition by combustion and its kinetic characteristics in a laboratory scale reactor. Environment Protection Engineering, 2015, 41(4): 143–150.
[19] Roh S.A., Kim W.H., Jung D.S., Hong B.K., Thermal destruction of HFC-134a in pilot-, and full-scale gasification systems. Journal of the Energy Institute, 2019, 92(6): 1842–1851.
[20] Zhang H., Liu C., Xu X., Li Q., Mechanism of thermal decomposition of HFO-1234yf by DFT study. International Journal of Refrigeration, 2017, 74: 399–411.
[21] Pu Y., Liu C., Li Q., Xu X., Huo E., Pyrolysis mechanism of HFO-1234yf with R32 by ReaxFF MD and DFT method. International Journal of Refrigeration, 2020,   109: 82–91.
[22] Frisch M.J., Trucks G.W., Schlegel H.B., Scuseria G.E., Robb M.A., Cheeseman J.R., Fox D.J., Gaussian 09. Gaussian, Inc.: Wallingford CT, 2009.
[23] Alecu I.M., Zheng J., Zhao Y., Truhlar D.G., Computational thermochemistry: scale factor databases and scale factors for vibrational frequencies obtained from electronic model chemistries. Journal of Chemical Theory and Computation, 2010, 6(9): 2872–2887.
[24] Sharma S., Abeywardane K., Goldsmith C.F., Theory-based mechanism for fluoromethane combustion I: Thermochemistry and abstraction reactions. The Journal of Physical Chemistry A, 2023, 127(6): 1499–1511.
[25] Jia W., Liu M., Lang X., Hu C., Li J., Zhu Z., Catalytic dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene over a modified NiO/Al2O3 catalyst. Catalysis Science & Technology, 2015, 5(6): 3103–3107. 
[26] Han T.U., Yoo B.S., Kim Y.M., Hwang B., Sudibya G.L., Park Y.K., Kim S., Catalytic conversion of 1,1,1,2-tetrafluoroethane (HFC-134a). Korean Journal of Chemical Engineering, 2018, 35(8): 1611–1619.

基金

This work was supported by the National Natural Science Foundation of China (52176011, 52236003) and the Creative Seed Fund of Shanxi Research Institute for Clean Energy, Tsinghua University.

版权

Science Press, Institute of Engineering Thermophysics, CAS and Springer-Verlag GmbH Germany, part of Springer Nature 2024
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