中文摘要：

在温度583~623 K、压力9.2~12.1 MPa和无催化剂的条件下,采用在线采样实验装置进行超临界甲醇与松脂反应动力学研究。建立了一套超临界甲醇与松脂反应动力学实验方法,利用毛细管柱气相色谱法在线跟踪测定反应体系浓度随时间的变化关系,按照物质结构和动力学相近原则划分复杂反应体系的集总组分,构建了超临界甲醇与松脂集总反应网络。以Matlab和Origin软件估算了动力学模型参数,得到单萜化合物脱氢、加氢、裂解,树脂酸酯化和裂解的活化能分别为117.38、76.56、67.62、153.74和126.05 kJ mol 1,所建立的动力学模型与实验数据吻合良好。

英文摘要：

The kinetics of reaction of supercritical methanol and oleoresin without catalyst at temperature range of 583 K to 623 K and under pressure of 9.2 MPa to 12.1 MPa was investigated by an experimental device with online sample analysis.A set of experimental methods for studying the kinetics of the reaction of supercritical methanol and oleoresin was established.The changes of the component concentration with reaction time were measured by tracking analysis of the capillary gas chromatograph.According to the principle of having similar material structures and kinetic characteristics,the reaction species were divided into several lumps.Then,the lumping reaction network for supercritical methanol and oleoresin was proposed.The kinetic model parameters were estimated by programming Matlab and Origin Statistics software,and the activation energies obtained are 117.38,76.56,67.62,153.74 and 126.05 kJ.mol.1 for dehydrogenation,hydrogenation and cracking of monoterpenoids,and esterification,cracking of resin acid,respectively.The results of the kinetic model calculation agree well with the experimental observations.