化学学报 ›› 2010, Vol. 68 ›› Issue (12): 1193-1198. 上一篇    下一篇

研究论文

奥克托金(HMX)的T-Jump/FTIR快速热裂解研究

任晓宁*,邵颖惠,王晓红,赵凤起,刘子如,张皋,衡淑云,谢明召   

  1. 西安近代化学研究所 西安 710065
  • 投稿日期:2009-07-01 修回日期:2009-11-02 发布日期:2010-02-03
  • 通讯作者: 任晓宁 E-mail:xueyexy@163.com

An Investigation on the Flash Pyrolysis Process of Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by T-Jump/FTIR Spectroscopy

REN Xiao-Ning, SHAO Ying-Hui, WANG Xiao-Hong, ZHAO Feng-Qi, LIU Zi-Ru, ZHANG Gao, HENG Shu-Yun, XIE Ming-Zhao   

  1. Xi an Modern Chemistry Research Institute, Xi an 710065
  • Received:2009-07-01 Revised:2009-11-02 Published:2010-02-03

采用T-Jump/FTIR快速热裂解原位红外光谱联用技术研究了奥克托金(HMX)在0.1, 0.2, 0.3和0.4 MPa的Ar气条件下, 以1000 ℃•s-1的升温速率快速升温至设定的反应温度, 用快速扫描傅立叶变换红外光谱跟踪分析分解产物的种类和相对摩尔浓度的变化, 研究了温度及压力对初始检测产物的影响. 结果表明, HMX在快速热裂解5 s过程中红外所检测到的主要气相产物为CO, CO2, NO, NO2, N2O, HCONH2, CH2O, H2O, HNCO及HCN, 并给出了这些产物相对摩尔浓度随时间变化的曲线. 根据气体产物相对摩尔浓度的比率N2O/HCN, 研究了压力和反应温度对HMX的快速热裂解过程及机理的影响, 认为在低温HMX分解的C—N键断裂在两竞争反应中占优, 通过压力的变化证明了气相产物之间存在二次反应.

关键词: 快速热裂解, T-Jump/FTIR, HMX, 压力

To investigate the thermal decomposition behavior of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetra- zocine (HMX), the T-Jump/FTIR spectroscopy was used to determine the main gaseous products released from the thermolysis of HMX in real time. HMX was flash-pyrolyzed at a heating rate of 1000 ℃•s-1 to set temperatures under Ar atmosphere of 0.1, 0.2, 0.3 and 0.4 MPa. With the help of rapid scanning fourier transform infrared (FTIR) spectroscopy to analysis the species and concentration of gaseous products of HMX, the effects of temperature and pressure on the initial products were studied. The results show that 10 specific IR-active gas products (CO, CO2, NO, NO2, N2O, HCONH2, CH2O, H2O, HNCO and HCN) for 5 s occur during the fast thermolysis process. The curves of concentration of the main gaseous products vs time were obtained. On the basis of N2O/HCN ratios, the effects of temperature and pressure on the thermolysis processes and on the decomposition mechanism of HMX were proposed. It is considered that C—N bond rupture in two competing branches for HMX decomposition is favored at lower temperature. The secondary reactions between the gaseous products are proved by the change of pressure.

Key words: flash pyrolysis, T-Jump/FTIR, HMX, pressure