孤岛减压渣油窄馏分的热反应动力学——Ⅰ.微分法和积分法确定动力学参数

THERMOLYSIS KINETICS OF NARROW FRACTIONS FOR GUDAO VACUUM RESIDUE Ⅰ. DETERMINATION OF KINETIC PARAMETERS BY OVERALL FIRST-ORDER DIFFERENTIAL METHOD AND INTEGRATING METHOD

在超临界流体萃取精密分馏装置上,将孤岛减压渣油分离为15个窄馏分。在升温速率为6℃/min和N_2气保护条件下,采用动态热重装置对各窄馏分进行热反应动力学研究,并运用总包反应微分法和积分法对各窄馏分的热重数据进行处理。研究发现,采用总包反应微分法和积分法时,孤岛1号至7号窄馏分在一定转化率范围内可用一级反应予以描述,两种方法得出的活化能分别介于59～65kJ/mol和65～68kJ/mol之间;8号至15号窄馏分采用分段一级反应进行拟合效果较好,第一段的活化能对两种方法分别介于59～139kJ/moI和64～133kJ/mol之间,第二段活化能分别介于136～205kJ/m01和88～190kJ/mol之间。

The 15 narrow fractions of Gudao residue were obtained by super critical fluid extraction technique. The nonisothermo-gravimetric techniques (overall first-order differential and integrating methods) have been applied to determine the kinetic parameters of the fractions with a heating rate of 6℃/min and under constant purge of N_2 through the reaction system. The results show that the narrow fraction No. 1 to 7 of Gudao residue can be treated by using the first-order kinetic model, the activation energy being 59～65 kJ/mol by the differential method and 65～68kJ/mol by the integrating method, respectively. The narrow fractions No. 8 to 15 fitted well of two independent first-order kinetic models at low and high conversions for the above two methods. The activation energy of thermolysis for the narrow fractions of No. 8 to 15 obtained by the differential method were 59～139 and 136～205kJ/mol for low and high conversion models, respectively; and those obtained by the integrating method were 64～133 and 88～190kJ/mol, respectively.