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过程工程学报 ›› 2023, Vol. 23 ›› Issue (10): 1421-1434.DOI: 10.12034/j.issn.1009-606X.222469

• 研究论文 • 上一篇    下一篇

基于分布活化能模型法的重油热解动力学对比研究

熊青安， 张玉明*， 李家州， 张炜， 陈哲文   

  1. 中国石油大学(北京)重质油国家重点实验室，北京 102249
  • 收稿日期:2022-12-27 修回日期:2023-03-12 出版日期:2023-10-28 发布日期:2023-10-30
  • 通讯作者: 张玉明 ymzhcup@163.com
  • 基金资助:
    国家自然基金;国家重点研发计划;国家自然基金;中国石油大学（北京）科研基金资助

Comparative study on pyrolysis kinetics of different heavy oil based on distributed activation energy model

Qing'an XIONG,  Yuming ZHANG*,  Jiazhou LI,  Wei ZHANG,  Zhewen CHEN   

  1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
  • Received:2022-12-27 Revised:2023-03-12 Online:2023-10-28 Published:2023-10-30

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摘要： 采用热重质谱联用技术，考察大港油浆(DG-SO)、青岛减压渣油(QD-VR)和加拿大油砂沥青(CA-OB)等三种重油的热解反应特性，分别采用Friedman法、FWO法和分布活化能模型(DAEM)求取重油热解反应的动力学参数。结果表明，饱和分和芳香分含量相对较高的DG-SO热解反应活性最高，胶质和沥青质含量相对较高的QD-VR热解反应活性最低。H2, CH4, CO和CO2等热解气体的释放曲线与重油热解的反应温度区间相对应，释放曲线的形状、强度和温度区间的差异主要归因于重油组成及其相应的热解反应活性。等转化率法中Friedman法的分析结果更准确，DG-SO, QD-VR和CA-OB在转化率0.1~0.9的平均反应活化能分别为80.15, 177.00和174.56 kJ/mol。单组分高斯型DAEM能够准确描述QD-VR的SARA(饱和分、芳香分、胶质和沥青质)转化率0~1区间的活化能，且计算得到它们的活化能分别为107.78, 210.88, 268.75和285.44 kJ/mol，而四组分高斯型DAEM法能够准确描述重油转化率0~1区间的活化能，且计算得到DG-SO, QD-VR和CA-OB的加权平均活化能分别为148.92, 205.92和190.37 kJ/mol。通过对比QD-VR的平均活化能及其SARA组分的平均活化能，发现重油热解过程中SARA各组分之间的相互作用导致其平均活化能与重油中芳香分的平均活化能相近。与此同时，通过对比QD-VR的虚拟四组分和其SARA组分的平均活化能，发现重油热解过程中胶质和沥青质的存在提高了饱和分和芳香分的平均活化能，而饱和分和芳香分的存在降低了胶质和沥青质的平均活化能。

关键词: 重油, 热解反应特性, 等转化率法, 分布活化能模型

Abstract: The pyrolysis behavior of Dagang slurry oil (DG-SO), Qingdao vacuum residue oil (QD-VR) and Canadian oil sand bitumen (CA-OB) were investigated by thermogravimetric mass spectrometry. The pyrolysis kinetic parameters were obtained by Friedman method, FWO method, and distributed activation energy model (DAEM), respectively. The results showed that DG-SO with relatively high content of saturates and aromatics had the highest pyrolysis reactivity, while QD-VR with relatively high content of resins and asphaltenes had the lowest pyrolysis reactivity. The releasing curves of H2, CH4, CO, and CO2 correspond to the main reaction temperature ranges of heavy oil pyrolysis. The distinctions of the shape, intensity and temperature range of the pyrolysis gases releasing curves between different types of heavy oils were mainly attributed to the corresponding composition and pyrolysis reactivity of each type of heavy oil. It was clearly found that Friedman method could gain more accuracy for description of pyrolysis process of heavy oil compared with FWO method in terms of equal conversion methods. The average activation energies (Ea) of DG-SO, QD-VR, and CA-OB were 80.15, 177.00, and 174.56 kJ/mol within the conversion range of 0.1~0.9, respectively. The one-component Gaussian DAEM could describe the whole process of SARA (saturates, aromatics, resins, asphaltenes), and their Ea were 107.78, 210.88, 268.75, and 285.44 kJ/mol, respectively. The four-component Gaussian DAEM could be used to precisely describe the whole pyrolysis process of heavy oil, and the calculated weighted average activation energies were 148.92, 205.92, and 190.37 kJ/mol, respectively. By comparing the Ea of QD-VR and its SARA components, it was found that the interaction between the SARA during the pyrolysis of heavy oil leaded to the Ea of QD-VR close to the Ea of aromatics in heavy oil. At the same time, it was found that the presence of resins and asphaltenes increased the average activation energy of saturates and aromatics, while saturates and aromatics reduced the average activation energy of resins and asphaltenes.

Key words: heavy oil, Pyrolysis behavior, iso-conversional method, Distributed activation energy model (DAEM)