硫酸羟胺的热分解动力学研究

摘要

The thermal stability properties and the thermal decomposition reaction kinetics of hydroxylamine sulfate (HAS) were studied at different heating rates (4 ℃/min, 7 ℃/min, and 10 ℃/min) by differential scanning calorimetry (DSC) in the range of RT (room temperature) - 400℃.The DSC data of the STA simultaneous thermal analyzer were analyzed by Advanced Kinetics and Technology Solutions (AKTS).Then the kinetics parameters including the activation energy, precxponential factor and reaction enthalpy were calculated by the thermal kinetics analysis method.The results showed that self-exothermic decomposition reaction occurred in the air atmosphere.The heat of reaction was 118.8 ±2.1 kJ/mol.The activation energy was calculated according to the Ozawa method, and its value was 82.45 k J/mol.Then the relations between differential conversional and activation energy ( or preexponential factor) were gained according to the Friedman method, and the reaction enthalpy was calculated as 116.2 ± 1.1 kJ/mol.Finally, the safety process of the hydroxylamine sulfate production was discussed.In the storage and transportation process, the temperature rising should be prevented, or else, the explosion accident of the hydroxylamine sulfate will be initiated by self-exothermic decomposition reaction.The experiment results could be used as reference and guide for the actual industry processes.%通过差示扫描量热(DSC)法研究了硫酸羟胺(HAS)的热稳定性能及其在不同温升速率(4℃/min、7℃/min、10℃/min)下的热分解动力学;由同步热分析仪(STA)测试得到的DSC热流数据,运用AKTS高级热动力学分析软件计算得到硫酸羟胺的活化能、指前因子和反应焓等热动力学参数.结果表明:硫酸羟胺在空气气氛中发生自分解放热反应,反应热为118.8±2.1kJ/mol;根据Ozawa法得到的活化能为82.45kJ/mol,并由Friedman法得到了不同转化率下的活化能E及指前因子A的关系,计算得到的反应热为116.2±1.lkJ/mol.最后,结合硫酸羟胺的生产工艺条件,对硫酸羟胺的安全生产工艺进行了分析讨论.在储存、运输过程中,应防止因温度变化而引发硫酸羟胺的自分解放热爆炸事故,实验研究结果对实际的工业生产过程具有一定的参考意义和指导价值.