CO_(2)诱导肼类燃料低温反应机理研究  

Reaction Mechanism Study of Hydrazine Fuels Induced by CO_(2)at Low Temperatures

作　　者：陈睿哲 刘永峰[1] 王龙[2] 毕贵军 宋金瓯[4] CHEN Rui-zhe;LIU Yong-feng;WANG Long;BI Gui-jun;SONG Jin-ou(Beijing Engineering Research Center of Monitoring for Construction Safety,Beijing University of Civil Engineering and Architecture,Beijing 102627,China;School of Chemical Engineering,Sichuan University,Chengdu 610065,China;Agency for Science,Technology and Research,Singapore 637662,Singapore;State Key Laboratory of Engines,Tianjin University,Tianjin 300072,China)

机构地区：[1]北京建筑大学北京市建筑安全监测工程技术研究中心,北京102627 [2]四川大学化学工程学院,成都610065 [3]新加坡科技研究局制造技术研究院,新加坡637662 [4]天津大学先进内燃动力全国重点实验室,天津300072

出　　处：《火炸药学报》2023年第5期427-435,I0011,共10页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.51976007);先进内燃动力全国重点实验室开放研究项目(No.K2023-04)。

摘　　要：为研究CO_(2)诱导肼类燃料在低温下的反应机理,采用量子化学计算对肼(N_(2)H_(4))、甲基肼(MMH)和偏二甲肼(UDMH)在不同温度下与CO_(2)的反应过程与势能面进行了分析。利用分子平均局部离子化能(ALIE)与福井函数/双描述符预测了N_(2)H_(4)、MMH和UDMH的反应活性位点,通过过渡态理论获得不同肼类燃料与CO_(2)反应的路径,构建其通道势能面,根据高精度能量获得宽温度范围下热力学参数与动力学数据。结果表明N_(2)H_(4)活性位点为N,MMH活性位点为与甲基相连的N,UDMH活性位点为氨基中的N;CO_(2)诱导肼类燃料低温反应的主要产物为肼羧酸,该反应为低温正向、高温逆向反应,这与常规燃料反应呈现相反的特点;在10 MPa压力下,N_(2)H_(4)的正逆向反应转变温度最小,约为400 K,MMH的正逆向反应转变温度约为460 K,而UDMH很难与CO_(2)反应;肼类燃料与CO_(2)的反应速率常数随温度升高而增大,其中MMH反应速率常数最大,在10 MPa、453 K环境下k为3.51×10^(-8)L/(s·mol)。In order to study the reaction mechanism of hydrazine fuels induced by CO_(2)at low temperatures,quantum chemical calculations were used to analyze the reaction processes and potential energy surfaces of hydrazine(N_(2)H_(4)),methyl hydrazine(MMH)and unsymmetrical dimethyl hydrazine(UDMH)with CO_(2)at different temperatures.The reactive sites of N_(2)H_(4),MMH and UDMH were predicted by using average local ionization energy(ALIE)and Fukui function/dual descriptor.To construct the channel potential energy surfaces,the transition state theory was used to obtain the reaction pathways of different hydrazine fuels with CO_(2).Thermodynamic parameters and kinetic data in a wide temperature range were obtained according to high precision energy.Results show that the active site of N_(2)H_(4)is the N atom,the active site of MMH is the N atom attached to methyl group,and the active site of UDMH is the N atom in amino group.The main product of the reaction of hydrazine fuels induced by CO_(2)is hydrazine carboxylic acid at low temperatures.This reaction is a low temperature forward and high temperature backward reaction,which shows the opposite characteristics to the conventional fuel reactions.The forward and backward reaction transition temperature of N_(2)H_(4)at 10 MPa is the lowest,about 400 K,and the corresponding temperature of MMH is about 460 K.UDMH is difficult to react with CO_(2).The reaction rate constants of hydrazine fuels with CO_(2)increase with increasing temperature,and the reaction rate constant of MMH is the largest with a value of 3.51×10^(-8)L/(s·mol)at 10 MPa and 453 K.

关 键 词：量子化学 肼类燃料 CO_(2)诱导 活性位点 肼(N_(2)H 4) 甲基肼(MMH) 偏二甲肼(UDMH) 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]