塔河常压渣油及其亚组分的非等温热转化反应性能研究

采用热重分析法对塔河常压渣油(THAR)及其亚组分的热转化反应性能进行了考察；在Sharp微分法基础上，采用分段动力学拟合，获得了渣油及其亚组分热转化速率峰值、速率峰值处的反应温度、转化率和剧烈裂解温度区间等动力学基本数据以及各亚组分的生焦性能。结果表明：各亚组分生焦率由低到高依次为饱和分＜芳香分＜胶质＜沥青质，沥青质是焦炭的主要来源；四组分按组成加权后的生焦率较THAR生焦率高4.21百分点，表明THAR亚组分混合物共焦化有利于抑制各亚组分的生焦；饱和分可促进其它亚组分生焦，而芳香分和胶质可抑制沥青质生焦，且芳香分的抑焦性能更强；在热转化反应过程中，裂化反应活性由高到低的顺序为饱和分＞芳香分＞胶质＞沥青质，各亚组分在低温段和高温段的活化能由低到高的顺序均为饱和分＜芳香分＜胶质＜沥青质，表明胶质和沥青质大分子的热转化过程需要提供较多的能量。

STUDY ON NON-ISOTHERMAL THERMOLYSIS OF TAHE ATMOSPHERE RESIDUE AND ITS SUB-FRACTIONS

The behavior of non-isothermal thermolysis properties of Tahe atmospheric residue and its sub-fractions (SARA components) were investigated by thermogravimetric analysis. Based on the Sharp differential method, the kinetic parameters, such as maximum rate and its corresponding reaction temperature, conversion and severe cracking temperature range of residue and SARA, as well as the coke formation tendency of SARA were obtained by piecewise fitting. It is found that the coking rate of SARA was in the order of saturates＜aromatics＜resins＜asphaltenes, and the coke formation is mainly from asphaltenes. The weighted coke rate of the SARA component is 4.21 percentage points higher than that of the residue. This indicates that the mixing of SARA is conductive to suppress the coke formation and that saturates promote the coke formation from other groups, while aromatics and resins inhabit the coke formation from asphaltenes and aromatics is better. In the thermal cracking process, the thermal cracking activity is in the order of saturates＞aromatics＞resins＞asphaltenes, and the activation energy of SARA components in low and high temperature range is in the order of saturates＜aromatics＜resins＜asphaltenes, which shows that resins and asphaltenes need more energy during thermal cracking process.