吡蚜酮二水合物脱溶剂机理及动力学研究  

Desolvation mechanism and kinetics of pymetrozine dihydrate

作　　者：陈巍[1,2,3] 姚其超 吴迪 纪旭 林玮浩 曲思源 李九龙 李唱 周丽娜 CHEN Wei;YAO Qichao;WU Di;JI Xu;LIN Weihao;QU Siyuan;LI Jiuong;LI Chang;ZHOU Lina(School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China;National Engineering Research Center of Industrial Crystallization Technology,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China;Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),Tianjin 300072,China)

机构地区：[1]天津大学化工学院,天津300072 [2]天津大学化工学院国家工业结晶工程技术研究中心,天津300072 [3]天津化学化工协同创新中心,天津300072

出　　处：《化学工业与工程》2023年第5期30-39,共10页Chemical Industry and Engineering

基　　金：天津市大学生创新创业训练计划项目(202010056216)。

摘　　要：利用TGA/DSC热分析技术对吡蚜酮二水合物热分解过程进行了研究。结果表明,氮气氛围下,吡蚜酮二水合物脱水焓变为154 kJ·mol^(-1)。脱溶剂机理高度吻合A4三维成核生长模型(R^(2)>0.99)。此外,使用Flynn-Wall-Ozawa方程,从转化率与升温速率2个维度进行拟合,分别得到了不等的表观活化能与指前因子。为消除不同拟合方法带来的误差,得到可靠的动力学参数,多升温速率法拟合所有升温速率下的各转化率的数据,结果为Ea:44.85 (±6.59) kJ·mol^(-1)(95%置信),lg(A/min^(-1)):9.54 (±1.08)(95%置信),R^(2)=0.8141。为验证推算结果,比较拟合方法的准确性,引入Kissinger方法计算活化能及指前因子进行验证。验算结果支持多升温速率法结论。This research analyzed the thermal desolvation mechanism and kinetics of pymetrozine di-hydrate by TGA/DSC.The result showed that in nitrogen atmosphere,the desolvation enthalpy of py-metrozine dihydrate desolvation is 154 kJ·mol^(-1).The pymetrozine dihydrate’s desolvation process matched with the 3-dimensional nucleation and growth model(Avrami-Erofeev equation,n=4)well(R^(2)>0.99)in this case.The Flynn-Wall-Ozawa equation was used to analyse the correlation of conver-sion rate and temperature changing rate,respectively.It revealed different apparent activation energy and pre-exponential factor A by two correlation methods.By fitting all the data of various temperature chan-ging rates and conversion rates,the various heating rate method can fix the two fitting methods’deviation and reveal credible data.It revealed apparent activation energy at 44.85(±6.59)kJ·mol^(-1)(95%confi-dence)and lg(A/min-1)at 9.54(±1.08)(95%confidence),R^(2)=0.8141.To certify the data and compare the fitting methods,Kissinger method was used to obtain apparent activation energy and a pre-exponential factor A.The verification sustained the conclusion by the various heating rate method.

关 键 词：吡蚜酮 溶剂化物 脱溶剂动力学 热分析 

分 类 号：TQ026.9[化学工程]