间苯三酚法合成TATB反应安全风险评估及热分析  

Risk Assessment and Thermal Analysis of the Synthesis of TATB by the Phloroglucinol Method

作　　者：张鹏 李新锐 李天宇 刘慧 许诚[2] 郭浩 陈松 吕智星 ZHANG Peng;LI Xin-rui;LI Tian-yu;LIU Hui;XU Cheng;GUO Hao;CHEN Song;LüZhi-xing(China Safety Technology Research Academy of Ordnance Industry,Beijing 100053,China;Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

机构地区：[1]中国兵器工业火炸药工程与安全技术研究院,北京100053 [2]西安近代化学研究所,西安710065

出　　处：《火炸药学报》2024年第11期1046-1054,I0004,共10页Chinese Journal of Explosives & Propellants

摘　　要：为了辨识间苯三酚法合成1,3,5-三氨基-2,4,6-三硝基苯(TATB)的工艺安全风险,开展了反应安全风险评估;基于风险矩阵法和特征温度分级法,利用差示扫描量热仪、反应量热仪和绝热加速量热仪进行合成工艺中硝化反应、烷基化反应和胺化反应相关热风险参数测试,并对TMR_(ad)和T_(D24)进行了预测。结合反应机理研究了工艺条件下反应体系的放热特性,评估确定了工艺危险度;通过DSC法研究了1,3,5-三羟基-2,4,6-三硝基苯(TNPG)、1,3,5-三乙氧基-2,4,6-三硝基苯(TETNB)和TATB的热稳定性,采用Kissinger法和Ozawa法计算了非等温动力学参数及热力学参数。结果表明,硝化反应和烷基化反应工艺危险度为5级,风险较高,胺化反应工艺危险度可按照1级管理;TNPG、TETNB和TATB的机械感度与其表观活化能的大小具有一定相关性,物质的表观活化能越大,对机械刺激越钝感。To identify the risks of the phloroglucinol method for the synthesis of 1,3,5-triamino-2,4,6-trinitrobenzene(TATB),a safety risk assessment was conducted.Utilizing the risk matrix method and characteristic temperature grading method,the thermal risk parameters associated with nitration,alkylation,and amination reactions in the synthesis process were tested using differential scanning calorimeter,reaction calorimeter,and adiabatic accelerating calorimeter,and the values of TMR_(ad) and T_(D24) were also predicted.Combining with the study of reaction mechanisms and the exothermic characteristics of the reaction systems under process conditions,the process hazard level was assessed.The thermal stabilities of 1,3,5-trihydroxy-2,4,6-trinitrobenzene(TNPG),1,3,5-triethoxy-2,4,6-trinitrobenzene(TETNB),and TATB were investigated by using DSC method.The non-isothermal kinetic parameters and thermodynamic parameters were calculated using Kissinger and Ozawa methods.Results show that the process hazard is rated as level 5 for both nitration and alkylation processes,indicating high explosion risk.While the process hazard is rated as level 1 for amination process.The mechanical sensitivity of TNPG,TETNB,and TATB demonstrate a certain correlation with their apparent activation energies.The greater the apparent activation energy,the less the sensitivity to mechanical stimulation.

关 键 词：安全工程 有机化学 1 3 5-三氨基-2 4 6-三硝基苯 TATB 风险评估 含能材料 钝感弹药 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O69[理学—化学]