基于模型预测和路径偏移的绝热反应动力学精确测算方法研究

绝热反应量热是绝热条件下研究反应动力学的热分析方法，在化学反应机理探究和风险评估方面日益成为最通用的自动化检测技术。但经典绝热反应量热系统中绝热程度有限、样品比热容难以测量的问题导致了动力学分析误差，国内外相关研究仍处于探索阶段。 . 本课题针对上述瓶颈问题提出一种不对称双通道绝热反应量热系统设计，拟通过有限元技术进行反应体系非稳态温度场分析，采用模型降维和等效简化方法开展基于模型预测的精确温度跟踪控制研究，抑制绝热侧样品反应热泄漏，使其获得近理想绝热反应过程，实现动力学精确分析前提；同时，利用参考侧反应单元不对称性设计，获得两通道路径偏移的反应过程数据，进而结合反应模型和比热容寻优方法精确测算动力学参数；最后研究系统原位校正和热分析性能评价方法，形成从绝热条件控制与测量、精确动力学分析到仪器技术实现与评价的闭环研究。项目成果将推动绝热热分析仪器与技术的前沿发展。

Adiabatic reaction calorimetry is a thermal analysis method for reaction kinetics under adiabatic conditions. It has increasingly become the most popular automatic detection technology for the chemical reaction mechanism research and thermal risk assessment. However in the classical adiabatic reaction calorimetric system, limitation of the adiabatic degree and change of the sample’s specific heat capacity resulting in the kinetic analysis error. At present, relevant researches are still in the exploratory stage. . Aiming at the above problems, this project puts forward the design of an asymmetric dual channel adiabatic reaction calorimetric system. The unsteady temperature field of the reaction system will be analyzed by finite element simulation technology. The model predictive control for accurate temperature tracking will be studied based on model dimension reduction and equivalent simplification techniques, to suppress reaction heat leakage of the adiabatic side and to obtain the near-ideal adiabatic reaction process, so as to realize the premise of accurate kinetics analysis. Then precise measurement and calculation of the reaction kinetic parameters are to be carried out by using the two-channel.deviated reaction data obtained from the asymmetric design of the reference side reaction unit, combining with the optimizations of reaction model and specific heat capacity. Finally, the in-situ correction and thermal analysis performance evaluation of the system are to be studied to form a closed loop from adiabatic control and measurement, precise kinetics analysis to instrumentation and method evaluation. The results of this project will promote the development of adiabatic thermal analysis instruments and technologies.