化工学报 ›› 2018, Vol. 69 ›› Issue (11): 4746-4753.DOI: 10.11949/j.issn.0438-1157.20180478

• 催化、动力学与反应器 • 上一篇    下一篇

美国绿河油页岩中沥青热解特征及动力学

陆梦科1, 匡吴奇1, 钱刚1, 段学志1, 周兴贵1, Chen De2   

  1. 1. 化学工程联合国家重点实验室, 华东理工大学, 上海 200237;
    2. 挪威科技大学化学工程系, 挪威 特隆德霍姆N-7491
  • 收稿日期:2018-05-07 修回日期:2018-07-12 出版日期:2018-11-05 发布日期:2018-11-05
  • 通讯作者: 段学志
  • 基金资助:

    挪威国家石油公司VISTA项目;上海东方学者项目;上海启明星项目(17QA1401200)和111计划(B08021)。

Pyrolysis characteristics and kinetics of bitumen from Green River oil shale

LU Mengke1, KUANG Wuqi1, QIAN Gang1, DUAN Xuezhi1, ZHOU Xinggui1, CHEN De2   

  1. 1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
    2. Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim N-7491, Norway
  • Received:2018-05-07 Revised:2018-07-12 Online:2018-11-05 Published:2018-11-05
  • Supported by:

    supported by the VISTA (a research program funded by Statoil), the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning, the Shanghai Rising-Star Program (17QA1401200) and the 111 Project of the Ministry of Education of China (B08021).

摘要:

沥青是油页岩中的重要有机质,也是油页岩中油母质热解产油和气过程的重要中间产物,对其热解研究有利于加深油页岩/油母质热解理解。通过索氏萃取提取出了绿河油页岩中的沥青,并对其进行了不同升温速率下热解实验。基于热重(TGA)数据,使用Friedman法计算了沥青热解的活化能,并通过活化能分布特征,推测沥青热解可能包含三个过程。接着,使用双高斯函数对含有交叠峰的DTG曲线进行反褶积处理,分解成三个峰,依次对应每一个过程。使用最小二乘法获得了这三个过程的活化能、指前因子和反应模型通式,并将获得的通式与四类固态物质热解模型中的11种理想模型进行对比,辨识出上述三个过程均遵循n级反应模型。

关键词: 沥青, 油页岩, 热解, 动力学, 反应模型

Abstract:

Bitumen is an important organic matter in oil shale and also a vital intermediate product from pyrolysis of kerogen to oil and gas. Soxhlet extraction is employed to obtain bitumen from Green River oil shale, and thermogravimetric analysis (TGA) of the bitumen is carried out under different heating rates. Based on TGA data, isoconversional Friedman method is used to estimate activation energy of bitumen pyrolysis, and the characteristic of activation energy indicates that its pyrolysis most likely involves three processes. Then, bi-Gaussian function is used to deconvolute DTG curves with overlapping peaks into three independent peaks. Subsequently, non-linear least square method is performed to analyze the peaks to estimate activation energies, pre-exponential factors and general forms of reaction models of each process. Comparisons are then made between general forms of reaction models and 11 kinetics models based on four solid-state pyrolysis mechanisms to discriminate reaction models, and results show that the three processes all follow nth-order kinetics model.

Key words: bitumen, oil shale, pyrolysis, kinetics, reaction model

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