环保型介质HFO-1234ze(E)的分解路径及其化学反应速率分析  

Analysis of Decomposition Path and Chemical Reaction Rate of Environmentally Friendly Medium HFO-1234ze(E)

作　　者：柯锟 田双双 张晓星 许正望[1] 王宇非 Ke Kun;Tian Shuangshuang;Zhang Xiaoxing;Xu Zhengwang;Wang Yufei(Hubei Engineering Research Center for Safety Monitoring of New Energy and Power Grid Equipment Hubei University of Technology,Wuhan,430068,China;State Grid Hubei Power Company Huang shi Power Supply Company,Huangshi,435000,China)

机构地区：[1]湖北工业大学新能源及电网装备安全监测湖北省工程研究中心,武汉430068 [2]国网湖北省电力公司黄石供电公司,黄石435000

出　　处：《电工技术学报》2021年第17期3553-3563,共11页Transactions of China Electrotechnical Society

基　　金：国家自然科学基金(51977159);湖北省自然科学基金(2020CFB398)资助项目。

摘　　要：近年来,HFO-1234ze(E)被电力行业研究者们视为一种具有较大潜力应用于中低压电气设备中的新型环保气体,但是对该分子的分解过程及化学反应速率还缺乏研究。该文首先基于密度泛函理论(DFT)计算了HFO-1234ze(E)的基本性质、气体分子断键和成键的规律、反应的焓值变化和化学反应速率,推断出可能的分解及其复合路径,并对分解产物的频率特性进行分析;最后通过工频击穿放电试验,采用气相色谱质谱联用仪(GC-MS)对分解产物进行定性分析。研究发现HFO-1234ze(E)分子的初步解离途径主要为C=C双键、C-H以及C-F单键;自由基F产生的路径较多,且相应的焓值变化较低,在分解过程中占主导地位;通过化学反应速率的计算,发现C-H键反应较为容易发生,验证了C-H键具有较高的化学反应活性且反应中存在大量自由基H;对分解产物的频率特性分析发现,除顺式C_(3)H_(2)F_(4)以外均具有稳定的结构,同时试验分解产生的CF_(4)、C_(2)F_(6)和C_(3)F_(6)等产物,与仿真结果基本相一致,验证了仿真计算结果。In recent years,HFO-1234ze(E)(C3H2F4)has been regarded by researchers in the electric power industry as a new environmental gas with great potential for application in low and middle voltage equipment.However,the decomposition process of the molecule and the chemical reaction rate of the product have not been studied.Based on density functional theory(DFT)to calculate the HFO-1234ze(E)the basic properties,the law of bond breaking and bonding of gas molecules,the enthalpy change of the reaction,and the chemical reaction rate.Infer the possible decomposition and its compound path,and analyze the frequency characteristics of the decomposition products.Finally,through the power frequency breakdown discharge test.Using gas chromatography mass spectrometer(GC-MS)to qualitatively analyze the decomposition products.It was found that the primary dissociation pathways of HFO-1234ze(E)molecule were mainly C=C double bond,C-H and C-F single bond.The free radical F has more paths,and the corresponding enthalpy change is lower,and it is dominant in the decomposition process.Through the calculation of the chemical reaction rate,it is found that the C-H bond reaction is easier to occur,which verifies that the C-H bond has high chemical reactivity and a large number of free radicals H.Analysis of the frequency characteristics of the decomposition products found that all products except cis-C_(3)H_(2)F_(4) have stable structures.At the same time,the CF_(4),C_(2)F_(6),C_(3)F_(6) and other products produced by the decomposition test are basically consistent with the simulation results,which verifies the simulation calculation.

关 键 词：HFO-1234ze(E) 环保气体 密度泛函理论 分解路径 化学反应速率 

分 类 号：TM213[一般工业技术—材料科学与工程]