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清华大学能源与动力工程系 热科学与动力工程教育部重点实验室
纸质出版日期:2023,
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许云婷, 张凯, 戴晓业, 等. HFC-134a氧化热解的机理和实验研究[J]. 制冷学报, 2023,44(3).
XU YUNTING, ZHANG KAI, DAI XIAOYE, et al. Mechanism and Experimental Studies of HFC-134a Oxidative Decomposition Mechanism. [J]. Journal of refrigeration, 2023, 44(3).
许云婷, 张凯, 戴晓业, 等. HFC-134a氧化热解的机理和实验研究[J]. 制冷学报, 2023,44(3). DOI: 10.3969/j.issn.0253-4339.2023.03.029.
XU YUNTING, ZHANG KAI, DAI XIAOYE, et al. Mechanism and Experimental Studies of HFC-134a Oxidative Decomposition Mechanism. [J]. Journal of refrigeration, 2023, 44(3). DOI: 10.3969/j.issn.0253-4339.2023.03.029.
我国面临巨大HFCs制冷剂销毁压力,亟需研究高效且温和的HFCs制冷剂降解方法。本文结合实验与量子化学计算,以典型HFCs制冷剂HFC-134a为研究对象,以降解率为主要衡量标准,研究制冷剂降解的高效途径。从量子化学的角度,研究了HFC-134a自热分解与氧化热解条件下的反应路径,在两条路径下,均易产生CHF=CF2与HF等可检测到的稳定产物。自热分解过程中,第一步化学键的断裂是决速步骤。氧化热解路径相较自热分解路径,反应能垒低,有利于反应快速发生。从实验的角度,发现在240~360 ℃温度范围内,随着温度的提高,HFC-134a的降解率由11%提高至66%,通过反应动力学常数拟合计算,得到HFC-134a的指前因子为7471.04 s-1,表观反应活化能为54.16 kJ/mol,与模拟计算所得化学反应能垒相吻合。
There is significant emphasis on the destruction of HFC refrigerants in China
culminating in an urgent need to explore efficient and mild HFC refrigerant degradation methods. In this study
a typical HFC refrigerant
HFC-134a
was chosen as the object of combined experimental studies and quantum chemical calculations
and the degradation rate was considered the main criterion for exploring the high-level pathway of refrigerant degradation. In terms of quantum chemistry
the reaction paths of HFC-134a under pyrolysis and oxidative decomposition conditions were explored. Under both paths
detectable stable products such as CHF=CF2 and HF were easily produced. During pyrolysis
the first step in the chemical bond cleavage is the rate-determining step. Compared to the pyrolysis path
the oxidative decomposition path has a lower reaction energy barrier
which is conducive to the rapid occurrence of the reaction. Experimental results showed that the degradation rate of HFC-134a increased from 11% to 66% with the increase in temperature in the range of 240–360 ℃. By fitting the kinetic constant of the reaction
the pre-exponential factor (A) of HFC-134a was determined as 7471.04 s-1
and the activation energy (Ea) was 54.16 kJ/mol
which were consistent with the simulated chemical reaction energy barrier.
反应能垒表观反应活化能氧化热解密度泛函方法HFC-134a
chemical reaction energy barrieractivation energy(s)oxidative decompositiondensity functional theory (DFT)HFC-134a
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