2,6-二苦氨基-3,5-二硝基吡啶合成过程硝化反应安全风险分析  

Security Risk Analysis of the Nitration in the Synthesis Process for 2,6-Bis(picrylamino)-3,5-Dinitropyridine

作　　者：许诚[1] 王彬[1] 刘红利[1] 张红武[1] 张义迎 王伯周[1] 邓明哲[1] 翟连杰[1] XU Cheng;WANG Bin;LIU Hong-li;ZHANG Hong-wu;ZHANG Yi-ying;WANG Bo-zhou;DENG Ming-zhe;ZHAI Lian-jie(Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《火炸药学报》2023年第1期85-90,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.22105155)。

摘　　要：为了分析2,6-二苦氨基-3,5-二硝基吡啶(PYX)合成过程硝化反应的热危险性,以2,6-双(苦氨基)吡啶(PAP)为原料,经硝化反应制备得到了PYX,利用反应量热仪(RC1)测定了该硝化反应热数据,利用差示扫描量热仪和绝热量热仪分别对PAP、PYX和硝化液的热分解过程进行了测试,并计算了硝化液的分解反应动力学参数。结果表明,硝化反应的摩尔生成焓Δm H r为-686.8 kJ/mol,绝热温升ΔT ad为76.8 K;硝化反应的最大累积度为48.7%,发生冷却失效时,体系所能达到的最高温度MTSR为86.6℃;DSC测得PAP和PYX的分解峰温分别为312.74℃和377.77℃;利用绝热加速度量热仪(ARC)测得绝热条件下,硝化液的T D24为221.3℃;综合反应量热数据和绝热量热数据得出,该硝化反应发生冷却失效后有可能引起冲料,但触发其二次分解反应风险较低。因此,需设置加料、搅拌与温度的联锁和蒸发冷却装置。To analyze the thermal risk of the nitration in synthesis process for 2,6-bis(picrylamino)-3,5-dinitropyridine(PYX),PYX was prepared by nitration reaction using 2,6-bis(picrylamino)pyridine(PAP)as raw material.The reaction heat data were tested by reaction calorimeter(RC1).The thermal stabilities of PAP,PYX and nitrified liquid were tested by using differential scanning calorimeter(DSC).The adiabatic decomposition process of the nitration reaction was measured by accelerating rate calorimeter(ARC)and the kinetic parameters were also studied.The results show that the molar enthalpy of formation(Δm H r)of the nitration reaction is-686.8 kJ/mol,the adiabatic temperature rise(ΔT ad)is 76.8 K,and the max thermal accumulation is 48.7%.Under the thermal runaway condition,the maximum temperature of the synthesis reaction(MTSR)is 86.6℃.The decomposition peak temperatures of PAP and PYX are 312.74℃and 377.77℃from DSC,respectively.The T D24 value of the reaction mixture is 221.3℃determined by ARC under adiabatic condition.Combined with the reaction calorimetric data and adiabatic thermal data,the nitration reaction may cause bumping after cooling failure,but the risk of secondary decomposition reaction is low.Therefore,it is necessary to set up the feeding,mixing and temperature interlocking and evaporative cooling devices.

关 键 词：物理化学 2 6-双(苦氨基)-3 5-二硝基吡啶 PYX PAP 反应量热 热危险性 硝化反应 耐热炸药 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]