用DSC曲线数据估算硝化棉的C_nB和表观经验级数自催化分解反应热爆炸临界温升速率

Estimation of the Critical Rate of Temperature Rise for Thermal Explosion of C_n B and Apparent Empiric-order Autocatalytic Decomposing Reaction of Nitrocellulose from DSC Curves

采用非线性约束优化问题的信赖域算法,由不同升温速率(β)条件下硝化棉(NC,14.14%N)的DSC曲线数据得到了NC的n级自催化分解反应(Cn B)和表观经验级数自催化分解反应的动力学参数和动力学方程。并由计算得到的β→0时的onset温度(Te0),热爆炸临界温度(Tb),相应于Tb时的转化率(αb)和动力学参数值获得了NC的热爆炸临界温升速率值。结果表明,在非等温DSC条件下NC分解反应可用表观经验级数自催化反应速率方程dα/dt=1015.76exp(-170830/RT)(1-α)0.95+1015.76exp(-159070/RT)α1.81(1-α)1.16描述。NC由自催化分解转向热爆炸时的热爆炸临界温升速率值为0.060K/s。

The kinetic parameters and kinetic equations of the n-th autocatalytic decomposition reaction rate equations （CnB） and apparent empiric-order autocatalytic decomposition reaction for nitrocellulose （NC,14.14 ％ N）from DSC data at different heating rates （β） were obtained by the trust region approach.The critical rate of temperature rise of thermal explosion for NC were also obtained from the onset temperature （Te0） corresponding to heating rate β→0,the critical temperature of thermal explosion （Tb）,the conversion degree （αb） corresponding to Tb and kinetic parameters.The results show that the autocatalytic decomposition reaction of NC under the non-isothermal DSC conditions can be described by the apparent empiric-order equation dα/dt=1015.76exp（-170830/RT）（1-α）0.95＋1015.76exp（-159070/RT）α1.81 （1-α）1.16,and the critical rate of temperature rise of thermal explosion for NC when autocatalytic decomposition converts into thermal explosion is 0.060 K · s-1.