苯氨基甲酸甲酯热解制备苯基异氰酸酯的非等温动力学  

Non-isothermal Decomposition Kinetics of Methyl N-Phenyl Carbamate for Preparation of Phenyl Isocyanate

作　　者：朱干宇[1,2] 李会泉[1] 邬慧雄 曹妍[1] 柳海涛[1] 李新涛[1,2] 张琴花[1,2] 唐清[1] 

机构地区：[1]中国科学院过程工程研究所绿色过程工程实验室,湿法冶金清洁生产技术国家工程实验室,北京100190 [2]中国科学院研究生院,北京100049 [3]华陆工程科技有限责任公司,陕西西安710054

出　　处：《过程工程学报》2012年第4期608-612,共5页The Chinese Journal of Process Engineering

基　　金：国家科技支撑重大基金资助项目(编号:2006BAC02A08);中国科学院知识创新工程重要方向基金资助项目(编号:KGCX2-YW-215)

摘　　要：采用热分析与红外联用技术对苯氨基甲酸甲酯(MPC)热解历程进行分析,结果表明,苯氨基甲酸甲酯的热解过程是一步生成苯基异氰酸酯同时释放出甲醇气体.进一步对该热解反应进行了非等温动力学研究,对MPC的热解数据采用Flynn-Wall-Ozawa法计算得到反应活化能.采用5种方法考察反应动力学参数,结果表明,MPC热解机理为相边界反应模型,机理函数为G(α)=α^(1/3),热解反应活化能E=20.52kJ/mol,指前因子lgA=2.23,动力学方程为α^(1/3)=169.82exp[20.52×10~3/(8.314T)]t.The decomposition process of methyl N-phenyl carbamate（MPC） was studied by TG-DTG,DSC and IR techniques.It is shown that the decomposition of MPC for generating phenyl isocyanate（PI） is one step with the generation of methanol gas.Then non-isothermal decomposition kinetics of MPC was studied.Flynn-Wall-Ozawa method was used to calculate the reaction activation energy,E,through the data of DSC/TG/DTG.The kinetic parameters were calculated using five kinetic analytical methods.The result indicated that the mechanism function of MPC decomposition was G（α）=α1/3,E and the pre-exponential factor,A,of the reaction were E=20.52 kJ/mol and lgA=2.23,respectively,and the kinetic equation could be expressed as α1/3=169.82exp[20.52×10~3/（8.314T）]t.

关 键 词：苯氨基甲酸甲酯 非等温 热解 动力学 热分析 

分 类 号：O643[理学—物理化学]